N-(carbonyl, carbonimidoyl, carbonothioyl) sulfonamide charge control agents and toners and developers

ABSTRACT

An electrophotographic toner having polymeric binder and a charge control agent selected from the group consisting of sulfonamides having the general structure: ##STR1## and metal salts thereof. T 1  is independently selected from H, alkyl having from 1 to 20 carbons, cycloalkyl having from 3 to 18 carbons, and aromatic and heteroaromatic ring systems having a solitary ring or 2 to 3 linked or fused rings. R 1  is O, S, N--H, N--R 5 , or N--L--R 5  ; where L is a linking group selected from: ##STR2## and R 5  is independently selected from alkyl having from 1 to 20 carbons, cycloalkyl having from 3 to 18 carbons, and aromatic and heteroaromatic ring systems having a solitary ring or 2 to 3 linked or fused rings. L 1  and L 2  are each independently a direct link or divalent alkyl or fluoroalkyl having from 1 to 20 carbons. R a  and R b  are each independently selected from the group consisting of H, F and ring systems having a solitary ring or from 2 to 3 fused or linked rings, said ring system having from 3 to 34 carbons, including carbons of substituent groups. If L 1  is a direct link, R a  is a ring system and if L 2  is a direct link, R b  is a ring system.

FIELD OF THE INVENTION

The invention relates to electrographic materials, particularly chargecontrol agents, and toners and developers incorporating those agents.This invention more particularly relates toN-(carbonyl,carbonimidoyl,carbonothioyl)sulfonamide charge controlagents and toners and developers including those agents.

BACKGROUND OF THE INVENTION

In electrography, image charge patterns are formed on a support and aredeveloped by treatment with an electrographic developer containingmarking particles which are attracted to the charge patterns. Theseparticles are called toner particles or, collectively, toner. Two majortypes of developers, dry and liquid, are employed in the development ofthe charge patterns.

In electrostatography, the image charge pattern, also referred to as anelectrostatic latent image; is formed on an insulative surface of anelectrostatographic element by any of a variety of methods. For example,the electrostatic latent image may be formed electrophotographically, byimagewise photo-induced dissipation of the strength of portions of anelectrostatic field of uniform strength previously formed on the surfaceof an electrophotographic element comprising a photoconductive layer andan electrically conductive substrate. Alternatively, the electrostaticlatent image may be formed by direct electrical formation of anelectrostatic field pattern on a surface of a dielectric material.

One well-known type of electrostatographic developer comprises a drymixture of toner particles and carrier particles. Developers of thistype are employed in cascade and magnetic brush electrostatographicdevelopment processes. The toner particles and carrier particles differtriboelectrically, such that during mixing to form the developer, thetoner particles acquire a charge of one polarity and the carrierparticles acquire a charge of the opposite polarity. The oppositecharges cause the toner particles to cling to the carrier particles.During development, the electrostatic forces of the latent image,sometimes in combination with an additional applied field, attract thetoner particles. The toner particles are pulled away from the carrierparticles and become electrostatically attached, in imagewise relation,to the latent image bearing surface. The resultant toner image can thenbe fixed, by application of heat or other known methods, depending uponthe nature of the toner image and the surface, or can be transferred toanother surface and then fixed.

Toner particles often include charge control agents, which, desirably,provide high uniform net electrical charge to toner particles withoutreducing the adhesion of the toner to paper or other medium. Many typesof positive charge control agents, materials which impart a positivecharge to toner particles in a developer, have been used and aredescribed in the published patent literature. In contrast, few negativecharge control agents, materials which impart a negative charge to tonerparticles in a developer, are known.

Prior negative charge control agents have a variety of shortcomings.Many charge control agents are dark colored and cannot be readily usedwith pigmented toners, such as cyan, magenta, yellow, red, blue, andgreen. Some are highly toxic or produce highly toxic by-products. Someare highly sensitive to environmental conditions such as humidity. Someexhibit high throw-off or adverse triboelectric properties in some uses.Use of charge control agents requires a balancing of shortcomings anddesired characteristics to meet a particular situation. There is thus acontinuing need for negative charge control agents which have improvedproperties.

U.S. Pat. No. 4,480,021 teaches the use as negative charge controlagents of sulfonamides and sulfones having the formula: R₁ --SO₂ --R₂ orR₃ --SO₂ --NH--R₄, in which R₁ is alkyl having from about 6 to about 22carbons or aryl, R₂ is aryl having from about 6 to about 18 carbons, R₃is aryl or alkyl group, and R₄ is alkyl, independent from R₃ having fromabout 6 to 22 carbons or aryl. Specific examples of aryl alkylsulfonamides were named: para-tolyl stearyl sulfonamide, para-tolylcetyl sulfonamide, para-xylyl stearyl sulfonamide, para-tolyl myristylsulfonamide, and isopropyl biphenyl stearyl sulfonamide.

U.S. Pat. No. 4,464,452 teaches toner compositions including a negativecharge control agent having the general structure: ##STR3## in which Rand R₁ are selected from H, alkyl, halo, nitro, "and the like". Thispatent also teaches as specific examples of negative charge controlagents: di-tolyl sulfonimide, phenyl tolyl sulfonimide, diphenylsulfonimide, di-1-naphthyl sulfonimide, hexadecyl tolyl sulfonimide,methyl tolyl sulfonimide, and dihexadecyl sulfonimide.

U.S. Pat. No. 3,577,345 teaches toners and developers including amaterial having the general structure: ##STR4## in which R is selectedfrom H, Cl, Br, aryl, alkyl having from 1 to 6 carbons; R' and R" areselected from H, aryl having from 1 to 12 carbons and alkyl having from1 to 12 carbons and chlorinated Ph--(Ph)n--Ph (n=0-3). This material isnot used as a charge control agent, but rather as an additive formodifying toner melt and viscosity. Similar melt and viscosity modifyingadditives are taught in U.S. Pat. Nos. 3,893,934 and 4,002,776. Thoseadditives have the general structure: ##STR5## in which one of R₁ and R₂is CH₃ and the other is H. These three patents do not teach or suggestwhether these materials are capable of functioning as charge controlagents for modification of charge. Charge control agents are commonlyused in the range of about 0.5 to 3.0 weight percent. The melt andviscosity additives, in these patents have concentrations in toners inthe range of about 10 to 40 weight percent.

U.S. Pat. No. 5,186,736 to Ong et al teaches toners having chargecontrol additives having the general structure ##STR6## where A and Bare independently selected from hydrogen, alkyl, alkoxy, carboxy, nitro,and halogen and X and Y are independently selected from hydrogen,hydroxy, alkyl, alkoxy, carboxy, nitro, and halogen and y is 0 or 1.

U.S. Pat. No. 5,186,736 to Ort et al teaches heterocyclicN-acylsulfonamide herbicides or growth regulators having the generalstructure: ##STR7## where R¹ is H or an aliphatic radical; R² and R³ areH, alkyl or phenyl; W is O, S, NR⁴ or NOR⁴ ; X is CHR², O or NR⁴ ; L isa (substituted) phenyl, napthyl, or monocyclic heteroaryl radical; A isa (substituted) pyrimidyl, triazinyl, triazolyl or bicyclic heteroarylradical; R⁴ is H, C₁ --C₃ -alkyl, C₁ --C₃ -haloalkyl, or phenyl; and mand n are 0 or 1.

SUMMARY OF THE INVENTION

The invention, in its broader aspects, provides an electrophotographictoner having polymeric binder and a charge control agent selected fromthe group consisting of sulfonamides having the general structure:##STR8## and metal salts thereof. T¹ is independently selected from H,alkyl having from 1 to 20 carbons, cycloalkyl having from 3 to 18carbons, and aromatic and heteroaromatic ring systems having a solitaryring or 2 to 3 linked or fused rings. R¹ is O, S, N--H, N--R⁵, orN--L--R⁵ ; where L is a linking group selected from: ##STR9## and R⁵ isindependently selected from alkyl having from 1 to 20 carbons,cycloalkyl having from 3 to 18 carbons, and aromatic and heteroaromaticring systems having a solitary ring or 2 to 3 linked or fused rings. L¹and L² are each independently a direct link or divalent alkyl orfluoroalkyl having from 1 to 20 carbons. R^(a) and R^(b) are eachindependently selected from the group consisting of H, F and ringsystems having a solitary ring or from 2 to 3 fused or linked rings,said ring system having from 3 to 34 carbons, including carbons ofsubstituent groups. If L¹ is a direct link, R^(a) is a ring system andif L² is a direct link, R^(b) is a ring system.

It is an advantageous effect of at least some of the embodiments of theinvention that negatively charging toners can be provided which havefavorable charging characteristics.

DESCRIPTION OF PARTICULAR EMBODIMENTS

The term "particle size" used herein, or the term "size", or "sized" asemployed herein in reference to the term "particles", means the medianvolume weighted diameter as measured by conventional diameter measuringdevices, such as a Coulter Multisizer, sold by Coulter, Inc of Hialeah,Fla. Median volume weighted diameter is the diameter of an equivalentweight spherical particle which represents the median for a sample; thatis, half of the mass of the sample is composed of smaller particles, andhalf of the mass of the sample is composed of larger particles than themedian volume weighted diameter.

The term "charge control" refers to a propensity of a toner addenda tomodify the triboelectric charging properties of the resulting toner.

The term "glass transition temperature" or "Tg" as used herein means thetemperature at which a polymer changes from a glassy state to a rubberystate. This temperature (Tg) can be measured by differential thermalanalysis as disclosed in "Techniques and Methods of Polymer Evaluation",Vol. 1, Marcel Dekker, Inc., New York, 1966.

The sulfonamides of the invention, which are useful as charge controlagents in electrophotographic toners, can be represented by the generalstructure: ##STR10## or the general structure: ##STR11## Alldesignations are defined below. The sulfonamides of the inventiongenerally can tautomerize, thus structure (4), for example; could, inmany cases, also be represented: ##STR12## For the sake of brevity,alternate tautomeric forms will not be illustrated herein, however,structural formulas should be understood to be inclusive of alternatetautomers. For example, the amido form of the following sulfonamide ofthe invention: ##STR13## (discussed below) should be understood toinclude the iminol form: ##STR14##

In all structural formulas herein, identical designations, for example:"R¹ " have the same meaning in all formulas, unless a more narrowdefinition is specifically indicated.

Compounds represented by formula (5) are salts of a metal "M" selectedfrom: Na, Mg, and K. The metal has a valence "e" of 1 or 2. Specificexamples of these materials are provided in Examples AP, AQ, and AR. Thesulfonamide metal salts of the invention are not currently preferred foruse as charge control agents because toner containing these materialsexhibited undesirably low charge levels.

T¹ is selected from H; alkyl having from 1 to 20 carbons, cycloalkylhaving from 3 to 18 carbons, and aromatic and heteroaromatic ringsystems having a solitary ring or 2 to 3, linked or fused rings. Thealkyl or ring system can be unsubstituted or can be substituted with thegroups described below in relation to R^(a) and R^(b).

Sulfonamides of the invention in which T¹ is not H, have, beendetermined to, surprisingly, be non-preferred for use as charge controlagents because of high throw-off and poor charge control. Specificexamples of such sulfonamides are provided in Examples AS, AT, and AU.When T¹ is H, general structure (4) reduces to: ##STR15##

In general structures (4), (5), and (6); R¹ is S, O, or NT². Therespective materials can be designated: for R¹ =O: N-(carbonyl)-(alkylor aryl)sulfonamides; for R¹ =S: N-((alkyl oraryl)sulfonyl)-carbothioamides or N-(cabonothioyl)-(alkyl oraryl)sulfonamides; and for R¹ =NT² : N((alkyl oraryl)sulfonyl)-carboximidamides or N-(carbonimidoyl)-(alkyl oraryl)sulfonamides.

T² represents H, R⁵ or --L--R⁵ where R⁵ is selected from alkyl havingfrom 1 to 20 carbons, cycloalkyl having from 3 to 18 carbons, andaromatic and heteroaromatic ring systems having a single ring or from 2to 3 linked or fused rings. The alkyl group or ring system can beunsubstituted or can be substituted with the groups described below inrelation to R^(a) and R^(b). L is a linking group selected from:##STR16##

R¹ =S or O is currently preferred over NT² and O is currently preferredover S for use as charge control agents. Sulfonamides of the inventionhaving the general structure: ##STR17## are thus not currentlypreferred. Examples of specific such sulfonamides are provided inExamples AV, AX, AY, AZ, and BA. Sulfonamides of the invention, whichhave the general structure: ##STR18## are not currently as highlypreferred as are sulfonamides of the invention in which R¹ is O.Specific examples of sulfonamides in which R¹ =S are theN-(phenylsulfonyl)-carbothiobenzamides illustrated by Examples BB andBC.

Taking into account the preferred groups for T¹ and R¹ reduces generalstructure (4) to: ##STR19##

In the sulfonamides of the invention, R^(a) and R^(b) are eachindependently selected from H or a ring system having a solitary ring or2 or 3 fused or linked rings. L¹ and L² are each independently a directlink or divalent alkyl or fluoroalkyl having from 1 to 20 carbons. If L¹or L² is a direct link, R^(a) or R^(b), respectively, is a ring systemor alkyl rather than H.

Each R^(a) or R^(b) ring system is cycloalkyl, aromatic, orheteroaromatic and has from 3 to 34 carbons counting carbons of anysubstituent group or groups. In most of the specific examples describedherein, R^(a) and R^(b) are phenyl, however, non-phenyl R^(a) and R^(b)aromatic groups are not currently disfavored. An example of asulfonamide in which R^(a) is a fused ring system is presented inExamples F1 and F2.

R^(a) and R^(b) groups, when a ring system, can be unsubstituted or canhave one or more substituents selected from the group: alkyl having from1 to 20 carbons, NO₂, NH₂, OH, COOH, cycloalkyl having from 3 to 6carbons, halo, alkoxy having from 1 to 20 carbons, alkycarbonyloxyhaving from 2 to 20 carbons and carboalkoxy having from 2 to 20 carbons.

Sulfonamides of the invention, in which R^(a) --L¹ -- and --L² --R^(b)are either or both alkyl are not currently preferred as charge controlagents. Examples of embodiments of such materials are compounds havingthe general structures: ##STR20## Specific examples of thesesulfonamides are presented in Examples BG and BH.

In embodiments of the sulfonamides of the invention, preferred for useas charge control agents, neither R^(a) nor R^(b) is H and L¹ and L² mayor may not be direct links. In a number of embodiments of the invention,L¹ and L² are both direct links and general structure (10) reduces to:##STR21## These materials can be referred to asN-(carbonyl)arylsulfonamides or N-aroylarylsulfonamides.

It is desirable that in the sulfonamides of the invention, R^(a) orR^(b) or both are phenyl and are substituted with one or more tertiaryalkyl or tertiary fluoroalkyl groups having from 4 to 8 carbons.Examples of specific t-alkyl substituted sulfonamides include ExamplesA-G, I-M, Q-Y, Z.A-Z.E, AA-AP, AX-AY, BA-BC, and BH. In the moredesirable of these Examples; A-G, I-M, Q-X, and AA-AO.B; R^(a) and R^(b)are both phenyl, R¹ is O, T¹ is H and that the t-alkyl is t-butyl.Linear alkyl substituted materials, for example, the material of ExampleH, are not presently preferred for use as charge control agents.

In a more desirable embodiment of the sulfonamides of the invention,R^(a) and R^(b) are phenyl and one of R^(a) and R^(b) is substitutedwith a tertiary alkyl group having from 4 to 8 carbons and the otherring is substituted with an electron withdrawing group, preferably NO₂,Cl, Br, F, CN, CO₂ R^(x) (where R^(x) is alkyl having from 1 to 20carbons), CF₃, or SO₂ CH₃. Specific examples of these materials includeExamples I-L and Q-W. In contrast, it is not preferred to have onlyelectron withdrawing substituents. This is demonstrated in Examples N-P.

Especially preferred are materials in which R^(a) and R^(b) are aryl andwhich are substituted with two t-alkyl or t-fluoroalkyl groups on one ofR^(a) and R^(b) and one or two electron withdrawing groups on the other.Currently preferred are phenyl R^(a) and R^(b) groups. Specific examplesincludes Examples Q-W. Suitable electron withdrawing groups for thisembodiment, may be selected on the basis of positive Hammett Sigmavalues, which represent a measure of the electronegativity of asubstituent relative to the unsubstituted derivative (wheresubstituent=H). (L. P. Hammett, Chem. Revs., Vol. 17, p. 125 et seq,(1935)) A Hammett Substituent value is defined relative to benzoic acid.By definition, for benzoic acids: sigma=log K-log K°, where K is theionization constant for a substituted benzoic acid in water at 25° C.and K° is the ionization constant for benzoic acid. σ is zero for H.Substituents with a σ greater than zero are more electronegative than H.Substituents with a σ less than zero are less electronegative than H.Hammett substituent values are problematic for ortho substituents.Hammett substituent values may or may not be additive for multiplesubstituents on a single ring. Examples of Hammett Sigma values arepresented in Table 1.

                  TABLE 1                                                         ______________________________________                                        Substituent    Hammett Sigma                                                  ______________________________________                                        para-NH.sub.2  -0.57                                                          para-OCH.sub.3 -0.28                                                          para-tert-butyl                                                                              -0.15                                                          para-CH.sub.3  -0.14                                                          H              0.00                                                           meta-OCH.sub.3 +0.10                                                          para-Cl        +0.24                                                          meta-Cl        +0.37                                                          para-COOCH.sub.3                                                                             +0.44                                                          para-COOH      +0.44                                                          meta-NO.sub.2  +0.71                                                          para-NO.sub.2  +0.81                                                          ______________________________________                                    

Not preferred are sulfonamides of the invention having two electronwithdrawing groups on one ring and a single t-alkyl group on the otherring, such as the sulfonamide of Example Y or having single substituentsof about the same electronegativity on each ring, as in Examples Z, C,and N.

Another preferred embodiment of the invention can be represented bygeneral structure (7): ##STR22## with the limitation that: R¹, L¹, L²,have the same meanings as above discussed; but R^(a) and R^(b) are botharomatic ring systems and at least one of R^(a) and R^(b) is a phenylmoiety having two t-butyl substituents and a third substituent.

In one particular embodiment, R^(a) or R^(b) is the moiety: ##STR23##where T is tertiary alkyl having from 4 to 8 carbons; and R is anelectron donating group. Suitable R groups include OH, NH₂, N(CH₃)₂,alkyl having from 1 to 8 carbons, and alkoxy having from 1 to 8 carbons.Branched and other relatively large R groups are not currently mostpreferred. Currently most preferred is an embodiment in which R^(a) orR^(b) is a phenyl substituted with two meta t-alkyl groups and a para OHgroup. The currently preferred t-alkyl groups are tert-butyl.

In another embodiment, R^(a) or R^(b) is the moiety: ##STR24## T istertiary alkyl having from 4 to 8 carbons and is preferably tert-butyl.

In both of these embodiments, the other one of R^(a) and R^(b) isunsubstituted; or is substituted with two meta t-alkyls and a para OH;or is substituted by one or more other substituents. Suitablesubstituents, in this embodiment, can be electron withdrawing orelectron donating. Examples of suitable substituents include: alkylhaving from 1 to 20 carbons, NO₂, NH₂, OH, COOH, cycloalkyl having from3 to 6 carbons, halo, alkoxy having from 1 to 20 carbons, andalkycarbonyloxy having from 2 to 20 carbons or carboalkoxy having from 2to 20 carbons.

Specific examples of sulfonamides of this embodiment of the inventionare provided in the Examples: in Example AA, L¹ is a direct link, R^(a)and R^(b) are phenyls, and R^(b) is substituted with two meta t-alkylgroups and a para OH group; in Examples AB--AN, L¹ and L² are bothdirect links, and R^(a) and R^(b) are each phenyl ring systems.

The following reaction scheme illustrates the preparation ofsulfonamides of the invention. The example sulfonamide prepared in thisscheme is N-(4-nitrobenzoyl)-4-t-butylbenzenesulfonamide: ##STR25## Thisscheme follows a general method disclosed in Kemp and Stephen, J. Chem.Soc., 1948, 11. Aromatic sulfonamide was acylated with an acid chloridein the presence of a 100 percent stoichiometric excess of pyridine.Equivalent procedures substituting appropriate starting materials can befollowed for the other sulfonamides of the invention, with the followingexceptions.

N-Arylsulfonylarylcarboximidamides and N-arylsulfonylarylcarbothioamidescan be produced from N-aroylarylsulfonamides by the following reactionscheme: ##STR26##

The following reaction scheme illustrates the preparation ofN-(3,5-di-t-butyl-4-hydroxybenzoyl)benzenesulfonamide and otherdi-t-butyl-hydroxy substituted sulfonamides: ##STR27## The following tworeaction schemes can be utilized, in appropriate examples, where thehydroxyl group is replaced by an acetoxy or the like: ##STR28##

Other sulfonamides, differing from those claimed herein, are describedin U.S. patent application Ser. No. 171,784, entitled: "BIS AND TRISN-(CARBONYL,CARBONIMIDOYL,CARBONOTHIOYL)SULFONAMIDE CHARGE CONTROLAGENTS, TONERS AND DEVELOPERS", filed concurrently with thisapplication, by inventors: John C. Wilson and Peter S. Alexandrovich,the disclosure of which is hereby incorporated by reference.

The toner of the invention includes charge control agent of theinvention, in an amount effective to modify, and preferably, improve theproperties of the toner. It is preferred that a charge control agentimprove the charging characteristics of a toner, so the toner quicklycharges to a negative value having a relatively large absolute magnitudeand then maintains about the same level of charge. Relatively largevalues of charge per mass that are currently preferred are in the 25-35microcoloumbs/gram range. Exceeding the upper end of the range canresult in low density on copy, and is thus not preferred. Thesulfonamides of the invention are negative charge control agents, thusthe toners of the invention, it is preferred, achieve and maintainnegative charges having relatively large absolute magnitudes.

It is also preferred that a charge control agent improve the chargeuniformity of a toner composition, that is, they insure thatsubstantially all of the individual toner particles exhibit atriboelectric charge of the same sign with respect to a given carrier.It is also preferred that toner throw-off be minimized. The term "tonerthrow-off" refers to the amount of toner powder thrown out of adeveloper mix as it is mechanically agitated, for example, within adevelopment apparatus. Throw-off can cause unwanted backgrounddevelopment and general contamination problems. It is further preferredthat the charge control agent used in a toner not be phase separatedwithin the toner (at least in so far as phase separation visible intoner melted onto a glass slide under a microscope at 650 timesmagnification). It has been determined empirically that such phaseseparation can correlate with increased clumping of the toner powder,and can lead to irreproducible manufacture of toner. It is alsopreferred that a charge control agent be colorless, particularly for usein light colored toners. The charge control agents of the invention arecolorless, with the exception of those in which R¹ =S. It is alsopreferred that a charge control agent be metal free and have goodthermal stability. The charge control agents of the preferredembodiments of the invention are metal free and have good thermalstability. Preferred materials described herein are based upon anevaluation in terms of a combination of characteristics rather than anysingle characteristic.

The properties of the thermoplastic polymers employed as the tonermatrix phase in the present invention can vary widely. Typically, andpreferably, amorphous toner polymers having a glass transitiontemperature in the range of about 50° C. to about 120° C. or blends ofsubstantially amorphous polymers with substantially crystalline polymershaving a melting temperature in the range of about 65° C. to about 200°C. are utilized in the present invention. Preferably, such polymers havea molecular weight distribution including an insoluble, very highmolecular weight fraction and one or more fractions having a numberaverage molecular weight in the range of about 1000 to about 500,000 anda weight average molecular weight in the range of about 2×10³ to about3×10⁶. Preferably, the thermoplastic polymers used in the practice ofthis invention are substantially amorphous. However, as indicated above,mixtures of polymers can be employed, if desired, such as mixtures ofsubstantially amorphous polymers with substantially crystallinepolymers.

Polymers useful as binders in the toner of the invention includestyrenic/acrylic copolymers. In general, preferred styrenic/acryliccopolymers have a glass transition temperature in the range of about 50°C. to about 100° C. In a particular embodiment of the invention, theresin is a copolymer of styrene and butyl acrylate, crosslinked withdivinyl benzene; produced in a suspension or emulsion polymerizationprocess. An initiator and, optionally, a chain transfer agent are usedin the synthesis. The ratio of styrene to butyl acrylate is in the rangeof from 90:10 to 60:40 and the divinyl benzene is used at a level of 3weight percent or less, preferably, at a level of about 0.1 to 1.0weight percent.

An optional but preferred component of the toner of the invention iscolorant: a pigment or dye. Suitable dyes and pigments are disclosed,for example, in U.S. Reissue Patent No. 31,072 and in U.S. Pat. Nos.4,160,644; 4,416,965; 4,414,152; and 2,229,513. One particularly usefulcolorant for toners to be used in black and white electrostatographiccopying machines and printers is carbon black. Colorants are generallyemployed in the range of from about 1 to about 30 weight percent on atotal toner powder weight basis, and preferably in the range of about 2to about 15 weight percent.

The toner of the invention can also contain other additives of the typeused in previous toners, including leveling agents, surfactants,stabilizers, and the like. The total quantity of such additives canvary. A present preference is to employ not more than about 10 weightpercent of such additives on a total toner powder composition weightbasis.

Dry styrenic/acrylic copolymer toners of this invention can optionallyincorporate a small quantity of low surface energy material, asdescribed in U.S. Pat. Nos. 4,517,272 and 4,758,491. Optionally thetoner can contain a particulate additive on its surface such as theparticulate additive disclosed in U.S. Pat. No. 5,192,637.

The charge control agent is incorporated into the toner. For example, ina dry electrostatographic toner, the charge control agent of theinvention can be mixed in any convenient manner, such as blending in themanner described in U.S. Pat. Nos. 4,684,596 and 4,394,430, with anappropriate polymeric binder material and any other desired addenda. Themixture is then ground to desired particle size to form a free-flowingpowder of toner particles containing the charge agent.

A preformed mechanical blend of particulate polymer particles, chargecontrol agent, colorants and additives can, alternatively, be rollmilled or extruded at a temperature sufficient to melt blend the polymeror mixture of polymers to achieve a uniformly blended composition. Theresulting material, after cooling, can be ground and classified, ifdesired, to achieve a desired toner powder size and size distribution.For a polymer having a T_(g) in the range of about 50° C. to about 120°C., or a T_(m) in the range of about 65° C. to about 200° C., a meltblending temperature in the range of about 90° C. to about 240° C. issuitable using a roll mill or extruder. Melt blending times, that is,the exposure period for melt blending at elevated temperature, are inthe range of about 1 to about 60 minutes. After melt blending andcooling, the composition can be stored before being ground. Grinding canbe carried out by any convenient procedure. For example, the solidcomposition can be crushed and then ground using, for example, a fluidenergy or jet mill, such as described in U.S. Pat. No. 4,089,472.Classification can be accomplished using one or two steps.

In place of melt blending or the like, the polymer can be dissolved in asolvent in which the charge control agent and other additives are alsodissolved or are dispersed. The resulting solution can be spray dried toproduce particulate toner powders. Limited coalescence polymersuspension procedures as disclosed in U.S. Pat. No. 4,833,060 areparticularly useful for producing small sized, uniform toner particles.

The toner particles have an average diameter between about 0.1micrometers and about 100 micrometers, and desirably have an averagediameter in the range of from about 4 micrometers to 30 micrometers forcurrently used electrostatographic processes. The size of the tonerparticles is believed to be relatively unimportant from the standpointof the present invention; rather the exact size and size distribution isinfluenced by the end use application intended. So far as is now known,the toner particles can be used in all known electrostatographic copyingprocesses.

The developers of the invention include carrier and toner of theinvention. Carriers can be conductive, non-conductive, magnetic, ornon-magnetic. Carriers are particulate and can be glass beads; crystalsof inorganic salts such as aluminum potassium chloride, ammoniumchloride, or sodium nitrate; granules of zirconia, silicon, or silica;particles of hard resin such as poly(methyl methacrylate); and particlesof elemental metal or alloy or oxide such as iron, steel, nickel,carborundum, cobalt, oxidized iron and mixtures of such materials.Examples of carriers are disclosed in U.S. Pat. Nos. 3,850,663 and3,970,571. Especially useful in magnetic brush development proceduresare iron particles such as porous iron, particles having oxidizedsurfaces, steel particles, and other "hard" and "soft" ferromagneticmaterials such as gamma ferric oxides or ferrites of barium, strontium,lead, magnesium, or aluminum. Such carriers are disclosed in U.S. Pat.Nos. 4,042,518; 4,478,925; and 4,546,060.

Carrier particles can be uncoated or can be coated with a thin layer ofa film-forming resin to establish the correct triboelectric relationshipand charge level with the toner employed. Examples of suitable resinsare the polymers described in U.S. Pat. Nos. 3,547,822; 3,632,512;3,795,618 and 3,898,170 and Belgian Patent No. 797,132. Other usefulresins are fluorocarbons such as polytetrafluoroethylene,poly(vinylidene fluoride), mixtures of these, and copolymers ofvinylidene fluoride and tetrafluoroethylene. See for example, U.S. Pat.Nos. 4,545,060; 4,478,925; 4,076,857; and 3,970,571. Polymericfluorocarbon coatings can aid the developer to meet the electrostaticforce requirements mentioned above by shifting the carrier particles toa position in the triboelectric series different from that of theuncoated carrier core material to adjust the degree of triboelectriccharging of both the carrier and toner particles. The polymericfluorocarbon coatings can also reduce the frictional characteristics ofthe carrier particles in order to improve developer flow properties;reduce the surface hardness of the carrier particles to reduce carrierparticle breakage and abrasion on the photoconductor and othercomponents; reduce the tendency of toner particles or other materials toundesirably permanently adhere to carrier particles; and alterelectrical resistance of the carrier particles.

In a preferred embodiment of the invention, the carrier is strontiumferrite coated with poly(methyl methacrylate) (PMMA) on a 2 percentweight/weight basis or strontium ferrite coated with dehydrofluorinatedand oxidized fluorocarbon as disclosed in U.S. Pat. No. 4,726,994, thespecification of which is hereby incorporated by reference herein. Thefluorocarbon is coated on a 0.5 percent weight/weight basis. Thefluorocarbon carrier is also referred to herein as "modified Kynar"

In a particular embodiment, the developer of the invention contains fromabout 1 to about 20 percent by weight of toner of the invention and fromabout 80 to about 99 percent by weight of carrier particles. Usually,carrier particles are larger than toner particles. Conventional carrierparticles have a particle size of from about 5 to about 1200 micrometersand are generally from 20 to 200 micrometers.

The toners of the invention are not limited to developers which havecarrier and toner, and can be used, without carrier, as single componentdeveloper.

The toner and developer of the invention can be used in a variety ofways to develop electrostatic charge patterns or latent images. Suchdevelopable charge patterns can be prepared by a number of methods andare then carried by a suitable element. The charge pattern can becarried, for example, on a light sensitive photoconductive element or anon-light-sensitive dielectric surface element, such as an insulatorcoated conductive sheet. One suitable development technique involvescascading developer across the electrostatic charge pattern. Anothertechnique involves applying toner particles from a magnetic brush. Thistechnique involves the use of magnetically attractable carrier cores.After imagewise deposition of the toner particles the image can befixed, for example, by heating the toner to cause it to fuse to thesubstrate carrying the toner. If desired, the unfused image can betransferred to a receiver such as a blank sheet of copy paper and thenfused to form a permanent image.

The invention is further illustrated by the following Examples andComparative Examples. Unless otherwise indicated, all starting materialswere commercially obtained. All melting points in the Examples andComparative Examples are uncorrected. Nuclear magnetic resonance (NMR)spectra were obtained in CDCl₃ or dimethylsulfoxide-d₆ with a VarianGemini-200 NMR spectrometer, marketed by Varian Associates, of PaloAlto, Calif. Elemental analyses were performed by combustion techniques,unless otherwise indicated and with the exception that metal analysesand bromine analyses were performed by neutron activation techniques.Thermogravimetric analyses were obtained with a Perkin-Elmer 7 seriesThermal Analysis System at a heating rate of 10° C./min in air from75°-400° C. Results are generally only reported here for colorlesstoners. Both black and blue toners were prepared for many of thesulfonamide charge control agents described herein, and results were inall cases, comparable to results with colorless toners.

In the Examples, a letter followed by a 1 designates a developer whichincludes PMMA coated carrier and a letter followed by a 2 designates adeveloper which includes a modified Kynar coated carrier. Letterdesignations in the Examples and Comparative Examples, correspond tosimilar letter designations of structural formulas. In Tables 2-19, "Ex"and "Com Ex" are the Example number or Comparative Example number,respectively; "CCA" is the designation of the structural formula of thecharge control agent; "m.p." is melting point; "Conc" is theconcentration of charge agent in styrene/n-butyl acrylate/divinylbenzenebinder resin, expressed in parts per hundred parts of binder resin("pph"), or weight percent ("wgt %"), as indicated; "P/S" is the visiblephase separation at 650X; "2 min" and "10 min" are the charge to massratios (Q/m) in microcoloumbs/gram at the indicated times; "bich"indicates simultaneous positive and negative charging; and "T.O. (mgadmix)" is throw-off in milligrams.

EXAMPLES EXAMPLES A1,A2

Preparation of Charge Control Agent

Sulfonamide charge control agent having the structural formula:##STR29## was prepared as follows. A mixture of 85.32 g (0.40 mol) of4-t-butylbenzenesulfonamide, 101.12 g (0.40 mol) of 3,5-t-butylbenzoylchloride and 63.28 g (0.80 mol) of pyridine was heated on a steam bathfor 1.5 hours and cooled. The reaction mixture was dissolved in 1 literof methylene chloride, washed 3 times with dilute HCl and once withwater. The solution was dried over magnesium sulfate and concentrated.The residue was recrystallized from 3 liters of ethanol, collected,washed with ethanol and dried to give 118.2 grams (68.8% of theoreticalyield) of product. The melting point for the product was determined tobe 232-234° C. Thermogravimetric analysis showed the product to bestable to 257° C.

A repetition of the above procedure yielded product having a meltingpoint of 231-232° C. Elemental analysis of that product gave: C=69.98,H=8.13, N=3.20, S=7.29. This compares to theoretical values of C=69.89,H=8.21, N=3.26, S=7.46. Nuclear magnetic resonance (NMR) in deuteratedchloroform was conducted and supported the above-indicated structuralformula for the product.

Preparation of Colorless Toners

A dry blend of 50.0 grams of poly(styrene-cobutylacrylate-co-divinylbenzene) and 0.5 grams of the sulfonamide chargecontrol agent A (structural formula A) was added to a heated two-rollcompounding mill. The roller surfaces were set to 150° C. The melt wasexercised on the mill for 20 minutes, then was removed and cooled. Theresulting slab was first coarse ground to 2 mm size on a laboratorymill, then finely pulverized to approximately 12 micrometer size on aTrost TX jet mill. The toner thus prepared had a concentration of chargecontrol agent of 1 part per hundred parts of styrene/n-butylacrylate/divinylbenzene binder resin. This procedure was repeated,varying the concentration of charge control agent to provideconcentrations of 2 and 4 parts per hundred (pph), on the same basis.

Preparation of Black Toners

The same procedures were followed as in the preparation of colorlesstoner having 1, 2, and 4 pph of charge control agent A, with theexception that 3.0 grams of Regal 300™ carbon black, marketed by CabotCorp., was added to the dry blend placed in the compounding mill and theslab produced was initially coarse ground to 2 mm size, before beingfinely pulverized.

Preparation of Blue Toners

The same procedures were followed as in the preparation of colorlesstoner having 1, 2, and 4 pph charge control agent A, with the exceptionthat 5 parts per hundred or copper phthalocyanine blue pigment from BASFCorp., was added to the dry blend placed in the compounding mill and theslab produced was initially coarse ground to 2 mm size, before beingfinely pulverized.

Preparation of Developers--PMMA Coated Carrier

Developer was prepared for each of the toners indicated above, by mixingtoner particles prepared as described above at a weight concentration of12% toner with carrier particles comprising strontium ferrite coresthinly coated (approximately 2 percent by weight) with poly(methylmethacrylate). The volume average particle size of the carrier particleswas from about 25 to 35 micrometers.

Preparation of Developers-Modified Kynar Coated Carrier

Developer was prepared for each of the toners indicated above, by mixingtoner particles prepared as described above at a weight concentration of12% toner with carrier particles comprising strontium ferrite coresthinly coated (approximately 0.5 percent weight/weight) withdehydrofluorinated and oxidized fluorocarbon as disclosed in U.S. Pat.No. 4,726,994. The volume average particle size of the carrier particleswas from about 25 to 35 micrometers.

Evaluation of Phase Separation

Colorless toners were smear melted onto microscope slides at 180° C. andwere examined microscopically at 650× magnification for evidence ofphase separation.

Evaluation of Toner Charging

Toner charge was then measured in microcoulombs per gram of toner (μc/g)in a "MECCA" device. Prior to measuring the toner charge, the developerwas vigorously shaken or "exercised" to cause triboelectric charging byplacing a 4 gram sample of the developer into a plastic vial, cappingthe vial and shaking the vial on a "wrist-action" robot shaker operatedat about 2 Hertz and an overall amplitude of about 11 cm for 2 minutes.Toner charge level after shaking was measured for each sample by placinga 100 milligram sample of the charged developer in a MECCA apparatus andmeasuring the charge and mass of transferred toner in the MECCAapparatus. This involves placing the 100 milligram sample of the chargeddeveloper in a sample dish situated between electrode plates andsubjecting it, simultaneously for 30 seconds, to a 60 Hz magnetic fieldand an electric field of about 2000 volts/cm between the plates. Thetoner is released from the carrier and is attracted to and collects onthe plate having polarity opposite to the toner charge. The total tonercharge is measured by an electrometer connected to the plate, and thatvalue is divided by the weight of the toner on the plate to yield thecharge per mass of toner (Q/m). The toner charge level (i.e.,charge-to-mass ratio) was also taken after exercising the developer foran additional 10 minutes by placing the magnetized developer in a glassbottle on top of a cylindrical roll with rotating magnetic core rotatingat 2000 revolutions per minute. The magnetic core had 12 magnetic polesarranged around its periphery, in an alternating north and southfashion. This closely approximates typical actual usage of the developerin an electrostatographic development process. After this additional 10minute exercising, the toner charge was measured in a MECCA apparatus.Values are reported in Tables 2-3 as Q/m 2 min. and 10 min.

Evaluation of Throw-Off

Throw-off values (T.O.) were determined by taking the 4 gram developersample at 12% toner concentration that had been exercised for 10 minutes(following the 2 minute exercising), admixing in 6% more toner toprovide a final toner concentration of about 18%), followed by 2 minutesmore exercise on the wrist action shaker. This developer was then placedon a roll containing a rotating magnetic core, similar to a magneticbrush roll used for electrostatic development. A Plexiglas housingcontained the assembly, and had a vacuum filter funnel mounted directlyover the roll. The weight of toner, in milligrams, collected on a pieceof filter paper after one minute of running the magnetic core at 2000revolutions per minute was reported as the throw-off value.

Results are presented in Tables 2-3.

EXAMPLES B1,B2-Z1,Z2

The same procedures were substantially followed as described in ExamplesA1-A2, except the following. In Examples F1-F2, G1-G2, N1-N2, Q1-Q2, T1-T2, and W1-W2 tetrahydrofuran was added to the reaction mixture. InExamples V1-V2, charge control agent having structural formula (V) wasprepared by permanganate oxidation of charge control agent havingstructural formula (E). In Examples X1-X2, charge control agent havingstructural formula (X) was prepared by catalytic reduction (highpressure hydrogenation) of charge control agent having structuralformula Q.

Only colorless toners were produced. Results are presented in Tables2-3. Sulfonamide charge control agents utilized in these examples areshown in the following structural formulas: ##STR30##

EXAMPLES Z.A1,Z.A2

Sulfonamide charge control agent having the structural formula:##STR31## was prepared as follows.

Preparation of 4-t-Octyltoluene

4-t-Octyltoluene was prepared as described in Journal of the AmericanChemical Society, Vol. 75, (1953) p. 6326.

Preparation of 4-t-Octylbenzoic acid

A mixture of 61.31 grams (0.30 mol) of 4-t-octyltoluene, 161.5 grams ofpyridine, and 80.8 grams of 32% KOH was heated on a steam bath. To thismixture was added, in 10 gram portions every 30 minutes, 117.22 grams(0.74 mol) of KMnO₄. The reaction mixture was heated overnight and then10 ml of ethanol was added. After 30 minutes, the mixture was filteredhot and the solid was washed with water. The combined filtrate andwashes were heated for another 10 minutes on a steam bath and filteredagain with water wash. The yellow filtrate comprised of two layers wasacidified with concentrated HCl. On cooling, the upper layercrystallized. This solid was collected, washed with water and dried. Thesolid was washed with Ligroine (bp=35-60° C.), dissolved in ether,washed with water, dried over MgSO₄ and concentrated. The residue wasrecrystallized from heptanes. Yield was 14.3 grams (20.34%). Meltingpoint=153-155° C. Elemental analysis found C=76.72, H=9.39. Thiscompares to calculated values for C₁₅ H₂₂ O₂ of C=76.88, H=9.46. An NMRspectrum, in CDCl₃, was obtained in which agreed with the structure ofthe expected product.

Preparation of N-(4-t-Octylbenzoyl)Benzernesulfonamide

A solution of 25.28 grams (0.10 mol) of 4-t-octylbenzoyl chlorideprepared from 4-t-octylbenzoic acid and oxaloyl chloride), 15.72 grams(0.10 mol) of benzenesulfonamide and 15.82 grams (0.20 mol) of pyridinewas heated on a steam bath for 1.75 hours and cooled. The reactionmixture was dissolved in methylene chloride, washed twice with diluteHCl, then with water and finally with aqueous sodium chloride solution.The solution was dried over MgSO₄ and concentrated. The solid wastreated with hot Ligroine (bp=35-60° C.), collected and dried. The solidwas recrystallized from 1:1 heptane:toluene. Yield was 26.43 grams(70.8%). Melting point=146-151.5° C. Elemental analysis found C=67.36,H=7.16, N=3.75, S=8.69. This compares to calculated values for C₂₁ H₂₇NO₃ S of C=67.53, H=7.29, N=3.75, S=8.58. An NMR spectrum was obtainedin which agreed with the structure of the expected product.

EXAMPLES Z.B1,Z.B2-Z.E1,Z.E2

The same procedures were substantially followed as described in ExamplesZ.A, except that starting materials in the aroylsulfonamide preparationwere different. Toners and developers were prepared as in ExamplesA1,A2. Results are presented in Tables 2-3. The structural formulas ofthe sulfonamides utilized in these examples are: ##STR32##

                  TABLE 2                                                         ______________________________________                                        Developer Using PMMA Coated Carrier                                                                                       T.O.                                          m.p.     Conc                   (mg                               Ex   CCA    (°C.)                                                                           (pph) P/S  2 min 10 min                                                                              admix)                            ______________________________________                                        A1   A      232-     1     N    -15.3 -39.5 1.2                                           234                                                               A1   A      232-     2     N    -17.5 -40.7 0.3                                           234                                                               A1   A      232-     4     N    -29.0 -31.2 0.2                                           234                                                               B1   B      221-     1     N    -13.4 -27.5 4.3                                           222                                                               B1   B      221-     2     N    -17.2 -23.6 1.6                                           222                                                               B1   B      221-     4     N    -24.6 -22.8 1.2                                           222                                                               C1   C      195-     1     N    -10.6 -35.8 6.4                                           197                                                               C1   C      195-     2     N    -13.2 -32.5 2.5                                           197                                                               C1   C      195-     4     N    -17.3 -32.1 1.1                                           197                                                               D1   D      192-     1     N    -12.9 -43.9 4.3                                           194                                                               D1   D      192-     2     N    -14.7 -39.9 4.4                                           194                                                               D1   D      192-     4     N    -19.1 -42.2 1.2                                           194                                                               E1   E      232-     1     N    -14.9 -44.7 3.3                                           233                                                               E1   E      232-     2     N    -23.2 -41.9 1.4                                           233                                                               E1   E      232-     4     N    -23.3 -41.8 1.2                                           233                                                               F1   F      236-     1     N    -18.4 -38.1 6.2                                           237                                                               F1   F      236-     2     N    -24.1 -33.4 4.0                                           237                                                               F1   F      236-     4     N    -32.2 -32.0 4.9                                           237                                                               G1   G      249      1     N    -20.5 -28.9 5.7                                           decomp                                                            G1   G      249      2     N    -24.6 -30.6 2.7                                           decomp                                                            G1   G      249      4     N    -28.2 -26.0 5.2                                           decomp                                                            H1   H      98-99    1     N    -13.3 -47.7 2.8                               H1   H      98-99    2     N    -14.4 -41.5 1.1                               H1   H      98-99    4     N    -14.8 -42.1 1.8                               I1   I      210-     1     N    -18.0 -34.0 3.1                                           212                                                               I1   I      210-     2     N    -19.7 -26.9 1.9                                           212                                                               I1   I      210-     4     N    -26.7 -22.3 1.9                                           212                                                               J1   J      231.5-   1     N    -20.5 -28.5 6.9                                           233                                                               J1   J      231.5-   2     N    -27.5 -25.6 2.4                                           233                                                               J1   J      231.5-   4     N    -35.3 -23.2 6.3                                           233                                                               K1   K      241.5-   1     N    -22.2 -26.4 3.4                                           243.5                                                             K1   K      241.5-   2     N    -27.4 -21.3 2.5                                           243.5                                                             K1   K      241.5-   4     N    -32.1 -19.0 1.0                                           243.5                                                             L1   L      214-     1     N    -16.5 -39.3 5.2                                           215.5                                                             L1   L      214-     2     N    -18.8 -37.1 3.7                                           215.5                                                             L1   L      214-     4     N    -36.7 -31.3 3.0                                           215.5                                                             M1   M      185-     1     N    -13.6 -32.6 4.1                                           187                                                               M1   M      185-     2     N    -18.4 -38.4 2.2                                           187                                                               M1   M      185-     4     N    -21.1 -36.0 2.8                                           187                                                               N1   N      223-     1     N    -14.2 -12.9 38.9                                          225                                                               N1   N      223-     2     N    -17.2 -8.1  58.8                                          225                                                               N1   N      223-     4     N    -13.4 -3.3  131.2                                         225                                                               O1   O      213-     1     N    -17.6 -20.0 6.0                                           214                                                               O1   O      213-     2     N    -18.8 -15.5 10.2                                          214                                                               O1   O      213-     4     N    -20.2 -13.1 27.5                                          214                                                               P1   P      199-     1     N    -20.8 -29.7 4.9                                           201                                                               P1   P      199-     2     N    -18.7 -20.3 5.0                                           201                                                               P1   P      199-     4     N    -20.8 -19.9 5.2                                           201                                                               Q1   Q      267-     1     N    -26.8 -26.5 1.5                                           268                                                               Q1   Q      267-     2     N    -39.5 -22.6 1.5                                           268                                                               Q1   Q      267-     4     N    -47.6 -23.5 1.4                                           268                                                               R1   R      236-     1     N    -21.5 -24.6 0.9                                           237                                                               R1   R      236-     2     N    -38.0 -30.9 1.1                                           237                                                               R1   R      236-     4     N    -51.9 -30.2 0.6                                           237                                                               S1   S      195-     1     N    -15.7 -33.5 1.7                                           197                                                               S1   S      195-     2     N    -18.9 -29.6 0.7                                           197                                                               S1   S      195-     4     N    -21.8 -27.7 1.0                                           197                                                               T1   T      249-     1     N    -22.5 -23.6 0.7                                           251                                                               T1   T      249-     2     N    -32.9 -24.9 0.8                                           251                                                               T1   T      249-     4     N    -40.0 -25.3 0.8                                           251                                                               U1   U      225-     1     N    -14.8 -35.7 2.0                                           227.5                                                             U1   U      225-     2     N    -28.3 -31.7 0.7                                           227.5                                                             U1   U      225-     4     N    -37.0 -31.8 0.9                                           227.5                                                             V1   V      289      1     Y    -16.8 -20.5 4.3                               V1   V      289      2     Y    -20.1 -21.5 2.0                               V1   V      289      4     Y    -24.8 -24.6 1.2                               W1   W      193-     1     N    -16.5 -35.7 1.7                                           198                                                               W1   W      193-     2     N    -18.2 -32.3 1.6                                           198                                                               W1   W      193-     4     N    -29.6 -29.8 1.2                                           198                                                               X1   X      251      1     Y    -19.1 -33.0 4.2                               X1   X      251      2     Y    -20.5 -27.3 1.0                               X1   X      251      4     Y    -22.9 -23.6 2.0                               Y1   Y      113-     1     N    -11.3 -31.7 6.5                               Y1   Y      113-     2     N    -14.1 -30.3 4.3                               Y1   Y      113-     4     N    -15.7 -32.3 5.7                               Z1   Z      145.5-   1     N    -16.2 -29.5 4.9                                           146.5                                                             Z1   Z      145.5-   2     N    -17.7 -31.2 3.9                                           146.5                                                             Z1   Z      145.5-   4     N    -18.8 -23.9 2.5                                           146.5                                                             Z.A  Z.A    146-     1     N    -14.8 -34.9 1.8                               1           151.5                                                             Z.A  Z.A    146-     2     N    -14.6 -31.0 1.4                               1           151.5                                                             Z.A  Z.A    146-     4     N    -16.0 -27.7 1.4                               1           151.5                                                             Z.B  Z.B    114.5-   1     N    -16.0 -33.1 2.8                               1           118                                                               Z.B  Z.B    114.5-   2     N    -18.7 -29.4 2.4                               1           118                                                               Z.B  Z.B    114.5-   4     N    -19.9 -30.6 2.5                               1           118                                                               Z.C  Z.C    172-     1     N    -14.4 -37.9 1.1                               1           173.5                                                             Z.C  Z.C    172-     2     N    -15.5 -28.7 1.8                               1           173.5                                                             Z.C  Z.C    172-     4     N    -16.8 -28.7 1.3                               1           173.5                                                             Z.D  Z.D    137.5-   1     N    -18.1 -32.9 3.6                               1           141                                                               Z.D  Z.D    137.5-   2     N    -18.3 -26.0 1.1                               1           141                                                               Z.D  Z.D    137.5-   4     N    -22.2 -25.2 2.3                               1           141                                                               Z.E  Z.E    133-     1     N    -15.5 -29.7 2.5                               1           135                                                               Z.E  Z.E    133-     2     N    -20.9 -24.7 3.0                               1           135                                                               Z.E  Z.E    133-     4     N    -20.6 -22.1 4.0                               1           135                                                               ______________________________________                                    

                  TABLE 3                                                         ______________________________________                                        Developer Using Modified Kynar Carrier                                                                                    T.O.                                          m.p.     Conc                   (mg                               Ex   CCA    (°C.)                                                                           (pph) P/S  2 min 10 min                                                                              admix)                            ______________________________________                                        A2   A      232-     1     N    -8.8  -49.7 0.2                                           234                                                               A2   A      232-     2     N    -20.3 -55.6 0.2                                           234                                                               A2   A      232-     4     N    -26.4 -33.5 0                                             234                                                               B2   B      221-     1     N    -4.3  -36.4 0.2                                           222                                                               B2   B      221-     2     N    -9.0  -36.0 0.1                                           222                                                               B2   B      221-     4     N    -21.6 -38.9 0.4                                           222                                                               C2   C      195-     1     N    -6.2  -53.0 0.3                                           197                                                               C2   C      195-     2     N    -8.3  -53.5 0.3                                           197                                                               C2   C      195-     4     N    -10.6 -50.7 0.2                                           197                                                               D2   D      192-     1     N    -4.5  -64.0 0.3                                           194                                                               D2   D      192-     2     N    -8.5  - 58.2                                                                              0.5                                           194                                                               D2   D      192-     4     N    -18.6 -65.3 0.3                                           194                                                               E2   E      232-     1     N    -20.0 -66.4 0.3                                           233                                                               E2   E      232-     2     N    -23.3 -58.6 0.3                                           233                                                               E2   E      232-     4     N    -30.5 -56.8 0.3                                           233                                                               F2   F      236-     1     N    -12.8 -65.3 0.3                                           237                                                               F2   F      236-     2     N    -17.9 -46.3 0                                             237                                                               F2   F      236-     4     N    -26.5 -47.9 0.2                                           237                                                               G2   G      249      1     N    -16.4 -45.3 0.4                                           decomp                                                            G2   G      249      2     N    -24.2 -49.6 0.3                                           decomp                                                            G2   G      249      4     N    -35.8 -43.4 0.3                                           decomp                                                            H2   H      98-99    1     N    -6.6  -66.1 0.4                               H2   H      98-99    2     N    -6.1  -54.7 0.2                               H2   H      98-99    4     N    -7.4  -56.4 0.2                               I2   I      210-     1     N    --    --    --                                            212                                                               I2   I      210-     2     N    --    --    --                                            212                                                               I2   I      210-     4     N    -28.3 -16.6 2.3                                           212                                                               J2   J      231.5-   1     N    -6.7  -48.5 0.4                                           233                                                               J2   J      231.5-   2     N    -22.8 -30.7 1.5                                           233                                                               J2   J      231.5-   4     N    -42.2 -27.8 6.1                                           233                                                               K2   K      241.5-   1     N    -11.1 -52.8 0.7                                           243.5                                                             K2   K      241.5-   2     N    -23.4 -22.2 1.7                                           243.5                                                             K2   K      241.5-   4     N    -30.0 -14.9 4.7                                           243.5                                                             L2   L      214-     1     N    -3.9  -62.0 0.8                                           215.5                                                             L2   L      214-     2     N    -4.3  -46.0 0.8                                           215.5                                                             L2   L      214-     4     N    -19.4 -57.0 0.7                                           215.5                                                             M2   M      185-     1     N    -5.8  -56.9 0.8                                           187                                                               M2   M      185-     2     N    -9.6  -43.9 0.6                                           187                                                               M2   M      185-     4     N    -15.4 -50.6 0.3                                           187                                                               N2   N      223-     1     N    -6.0  -29.1 3.3                                           235                                                               N2   N      233-     2     N    -14.2 -12.7 13.6                                          235                                                               N2   N      233-     4     N    -11.7 -2.6  176.7                                         235                                                               O2   O      213-     1     N    -13.0 -39.1 0.5                                           214                                                               O2   O      213-     2     N    -13.9 -10.0 5.2                                           214                                                               O2   O      213-     4     N    -14.6 -1.4  129.3                                         214                                                               PP2  P      199-     1     N    -8.8  -50.1 0.9                                           201                                                               P2   P      199-     2     N    -11.1 -18.3 3.7                                           201                                                               P2   P      199-     4     N    -16.2 -1.4  53.9                                          201                                                               Q2   Q      267-     1     N    -21.2 -40.2 0.3                                           268                                                               Q2   Q      267-     2     N    -28.1 -32.4 0.8                                           268                                                               Q2   Q      267-     4     N    -30.5 -32.7 1.2                                           268                                                               R2   R      236-     1     N    -12.6 -44.9 0.1                                           237                                                               R2   R      236-     2     N    -35.1 -51.1 0.4                                           237                                                               R2   R      236-     4     N    -58.2 -59.7 0.3                                           237                                                               S2   S      195-     1     N    -13.4 -57.4 0.2                                           197                                                               S2   S      195-     2     N    -11.4 -48.4 0.2                                           197                                                               S2   S      195-     4     N    -15.7 -47.6 0.3                                           197                                                               T2   T      249-     1     N    -21.1 -41.3 0.3                                           251                                                               T2   T      249-     2     N    -37.4 - 50.2                                                                              0.1                                           251                                                               T2   T      249-     4     N    -45.8 -53.0 0.2                                           251                                                               U2   U      225-     1     N    -5.3  -60.2 1.1                                           227.5                                                             U2   U      225-     2     N    -21.9 -45.5 0.6                                           227.5                                                             U2   U      225-     4     N    -45.7 -57.7 0.3                                           227.5                                                             V2   V      289      1     N    -7.5  -17.7 1.8                               V2   V      289      2     N    -9.6  -9.6  2.2                               V2   V      289      4     N    -14.1 -14.5 2.0                               W2   W      193-     1     N    -7.3  -59.7 0.4                                           198                                                               W2   W      193-     2     N    -8.7  -51.3 0.4                                           198                                                               W2   W      193-     4     N    -30.8 -45.6 0.3                                           198                                                               X2   X      251      1     N    -21.1 -44.1 0.5                               X2   X      251      2     N    -20.2 -35.4 1.0                               X2   X      251      4     N    -25.2 -34.1 1.3                               Y2   Y      113-     1     Y    -12.1 -51.7 0.5                                           115                                                               Y2   Y      113-     2     Y    -9.4  -43.3 0.2                                           115                                                               Y2   Y      113-     4     Y    -9.4  -38.5 0.5                                           115                                                               Z2   Z      145.5-   1     N    -5.1  -43.9 1.5                                           146.5                                                             Z2   Z      145.5-   2     N    -2.6  -36.6 1.7                                           146.5                                                             Z2   Z      145.5-   4     N    -2.5  -24.7 1.5                                           146.5                                                             Z.A  Z.A    146-     1     N    -10.2 -59.2 0.2                               1           151.5                                                             Z.A  Z.A    146-     2     N    -8.1  -50.9 0.0                               1           151.5                                                             Z.A  Z.A    146-     4     N    -8.4  -40.2 0.0                               1           151.5                                                             Z.B  Z.B    114.5-   1     N    -14.9 -59.0 0.2                               1           118                                                               Z.B  Z.B    114.5-   2     N    -12.9 -48.5 0.4                               1           118                                                               Z.B  Z.B    114.5-   4     N    -15.7 -39.5 0.1                               1           118                                                               Z.C  Z.C    172-     1     N    -8.7  -60.5 0.0                               1           173.5                                                             Z.C  Z.C    172-     2     N    -9.7  -53.2 0.0                               1           173.5                                                             Z.C  Z.C    172-     4     N    -11.1 -47.6 0.2                               1           173.5                                                             Z.D  Z.D    137.5-   1     N    -13.9 -63.7 0.2                               1           141                                                               Z.D  Z.D    137.5-   2     N    -15.4 -49.8 0.0                               1           141                                                               Z.D  Z.D    137.5-   4     N    -18.3 -37.5 0.4                               1           141                                                               Z.E  Z.E    133-     1     N    -14.5 -59.2 0.0                               1           135                                                               Z.E  Z.E    133-     2     N    -13.7 -49.7 0.3..                             1           135                                                               Z.E  Z.E    133-     4     N    -16.3 -37.2 0.4                               1           135                                                               ______________________________________                                    

EXAMPLES AA1,AA2

Sulfonamide charge control agent having the structural formula:##STR33## was prepared as follows.3-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid was prepared by themethod described in U.S. Pat. No. 4,205,176 from 2,6-di-t-butyl phenoland acrylonitrile in accord with the reaction scheme: ##STR34##3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl chloride was prepared from3-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid and oxalyl chloride inaccord with the reaction scheme: ##STR35## A mixture of4-chlorobenzedsulfonamide (9.58 g, 0.05 mol), 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl chloride (14.84 g, 0.05 mol), andtoluene (100 ml) was prepared and heated at reflux. A complete solutionwas obtained and acidic vapors were emitted. Refluxing was continued forabout 22.5 hours. After cooling, the solution was concentrated on arotary evaporator to obtain an oily residue. The residue was stirredwith ligroine (bp=35-60° C.), from which a crystalline precipitate wasobtained. The crystalline material was collected and recrystallized from100 ml of 1 to 1 heptane:toluene. The resulting solid was collected with1 to 1 heptane:toluene rinse, washed with ligroine (bp=35-60° C.) anddried. Yield was 17.9 grams (79.2%). Melting point was 166.5-171° C.Elemental analysis found C=60.63, H=6.59, N=3.00, Cl=8.19, S=7.08. Thiscompares to calculated values for C₂₃ H₃₀ ClNO₄ S of C=61.12, H=6.69,N=3.10, Cl=7.84, S =7.09. An NMR spectrum was obtained in deuteratedchloroform which agreed with the structure of the expected product.

The same procedures were substantially followed in the preparation oftoners and developers and in evaluating materials as described inExamples A, except that only colorless toners were produced. Results arepresented in Tables 4-5.

EXAMPLES AB1, AB2

Sulfonamide charge control agent having the structural formula:##STR36## was prepared in accord with the reaction scheme: ##STR37## asfollows. A mixture of 4-chlorobenzedsulfonamide (9.58 g, 0.050 mol),3,5-di-t-butyl-4-hydroxy-benzoyl chloride (13.44 g, 0.050 mol), andtoluene (100 ml) was prepared and heated at reflux. A complete solutionwas obtained and acidic vapors were emitted. Refluxing was continued forabout 18.5 hours. During this time, solid precipitated. At the end ofthis time, the evolution of acidic vapors had stopped. After cooling, awhite solid was collected, washed with ligroine (bp=35°-60° C.) anddried. This material was recrystallized from 550 ml of acetonitrile,collected and dried. Yield was 16.8 grams (79.25%). Melting point was260°-261.5° C. Elemental analysis found C=59.05, H=6.08, N=3.49,Cl=8.98, S=7.40. This compares to calculated values for C₂₁ H₂₆ ClNO₄ Sof C=59.49, H=6.18, N=3.30, Cl=8.36, S=7.56. An NMR spectrum, indeuterated chloroform, was obtained which agreed with the structure ofthe expected product.

The same procedures were substantially followed in the preparation oftoners and developers and in evaluating materials as described inExamples A, except that only colorless toners were produced. Results arepresented in Tables 4-5.

EXAMPLES AC1,AC2-AO.B1,AO.B2

The same procedures were substantially followed as described in ExamplesAB, except that starting materials in the aroylsulfonamide preparationwere different, Examples AE were prepared in xylenes as solvent, andExamples AN were prepared with pyridine and 4-dimethylaminopyridine intetrahydrofuran. Results are presented in Tables 4-5. Sulfonamidesutilized in these examples are indicated by the designations on thefollowing structural formulas: ##STR38##

EXAMPLES AO.C1,AO.C2

Sulfonamide charge control agent having the structural formula:##STR39## was prepared in accord with the reaction scheme: ##STR40## asfollows.

3,5-Di-t-butyl-2-nitrobenzoyl chloride was prepared by nitration of3,5-di-t-butylbenzoic acid 46.86 grams (0.20 mol) with 90% nitric acid(150 ml, d=1.5) to give 3,5-di-t-butyl-2-nitrobenzoic acid (54.6 grams)followed by treatment with thionyl chloride (250 ml) withdimethylformamide (1 ml).

A mixture of 3,5-di-t-butyl-2-nitro-benzoyl chloride (29.78 g, 0.10mol), 4-chlorobenzedsulfonamide (19.16 g, 0.10 mol), and pyridine (15.82grams, 0.20 mol) was prepared and heated on a steam bath, with stirring.After five minutes, 50 ml of tetrahydrofuran was added. Another 50 ml oftetrahydrofuran was added after 10 minutes. After about 1.5 hours, thereaction mixture was cooled and poured into dilute HCl. An oilyprecipitate crystallized, was collected, and was washed twice withwater. The product was recrystallized from isopropanol, collected anddried. Yield was 31.55 grams (69.7%). Melting point was 243°-248° C.Elemental analysis found C=55.39, H=5.62, N=6.25, Cl= 7.90, S=7.52. Thiscompares to calculated values for C₂₁ H₂₅ ClN₂ O₅ S of C=55.69, H=5.56,N=6.18, Cl=7.83, S=7.08. An NMR spectrum was obtained which agreed withthe structure of the expected product.

The same procedures were substantially followed in the preparation oftoners and developers and in evaluating materials as described inExamples A, except that only colorless toners were produced. Results arepresented in Tables 4-5.

                  TABLE 4                                                         ______________________________________                                        Developer Using PMMA Coated Carrier                                                                                       T.O.                                          m.p.     Conc                   (mg                               Ex   CCA    (°C.)                                                                           (pph) P/S  2 min 10 min                                                                              admix)                            ______________________________________                                        AA1  AA     166.5-   1     N    -12.6 -48.9 2.5                                           171                                                               AA1  AA     166.5-   2     N    -13.4 -44.8 1.7                                           171                                                               AA1  AA     166.5-   4     N    -15.4 -34.2 3.0                                           171                                                               AB1  AB     260-     1     N    -28.0 -32.3 1.1                                           261.5                                                             AB1  AB     260-     2     N    -30.5 -25.5 1.8                                           261.5                                                             AB1  AB     260-     4     N    -36.9 -21.7 1.6                                           261.5                                                             AC1  AC     205-     1     N    -17.1 -45.0 3.3                                           208                                                               AC1  AC     205-     2     N    -21.1 -41.0 2.9                                           208                                                               AC1  AC     205-     4     N    -27.1 -32.0 1.8                                           208                                                               AD1  AD     256-     1     N    -18.5 -40.6 0.4                                           258                                                               AD1  AD     256-     2     N    - 23.4                                                                              -30.4 0.5                                           258                                                               AD1  AD     256-     4     N    -30.4 -26.6 0.7                                           258                                                               AE1  AE     206-     1     N    -18.7 -43.9 0.7                                           212                                                               AE1  AE     206-     2     N    -25.9 -36.7 0.9                                           212                                                               AE1  AE     206-     4     N    -36.4 -26.2 1.2                                           212                                                               AF1  AF     222-     1     N    -20.3 -43.8 1.1                                           225.5                                                             AF1  AF     222-     2     N    -21.8 -34.6 2.7                                           225.5                                                             AF1  AF     222-     4     N    -32.0 -24.3 1.6                                           225.5                                                             AG1  AG     267-     1     N    -28.1 -36.8 0.8                                           268.5                                                             AG1  AG     267-     2     N    -34.7 -33.7 1.2                                           268.5                                                             AG1  AG     267-     4     N    -36.6 -23.8 1.2                                           268.5                                                             AH1  AH     224-     1     N    -21.3 -40.7 1.4                                           227                                                               AH1  AH     224-     2     N    -30.8 -33.5 1.3                                           227                                                               AH1  AH     224-     4     N    -34.3 -23.9 1.6                                           227                                                               AI1  AI     216.5-   1     N    -18.5 -45.8 0.9                                           218.5                                                             AI1  AI     216.5-   2     N    -24.7 - 34.8                                                                              1.7                                           218.5                                                             AI1  AI     216.5-   4     N    -29.3 -27.5 2.3                                           218.5                                                             AJ1  AJ     242-     1     N    -16.3 -41.4 0.9                                           245                                                               AJ1  AJ     242-     2     N    -22.9 -34.1 1.1                                           245                                                               AJ1  AJ     242-     4     N    -30.2 -28.1 2.0                                           245                                                               AK1  AK     192.5-   1     N    -19.9 -44.9 1.6                                           195                                                               AK1  AK     192.5-   2     N    -26.2 -46.8 1.0                                           195                                                               AK1  AK     192.5-   4     N    -29.4 -34.7 1.1                                           195                                                               AL1  AL     248.5-   1     N    -23.2 -44.0 0.9                                           249.5                                                             AL1  AL     248.5-   2     N    -25.6 -34.9 0.8                                           249.5                                                             AL1  AL     248.5-   4     N    -27.6 -27.7 1.1                                           249.5                                                             AM1  AM     245-     1     N    -18.2 -34.5 0.9                                           248                                                               AM1  AM     245-     2     N    -19.9 -29.5 1.5                                           248                                                               AM1  AM     245-     4     N    -22.0 -22.8 1.6                                           248                                                               AN1  AN     246-     1     N    -14.6 -36.4 2.8                                           248.5                                                             AN1  AN     246-     2     N    -22.7 -30.7 2.0                                           248.5                                                             AN1  AN     246-     4     N    -22.0 -20.3 0.8                                           248.5                                                             AO1  AO     186-     1     N    -13.2 -33.4 2.7                                           189                                                               AO1  AO     186-     2     N    -19.8 -34.8 0.9                                           189                                                               AO1  AO     186-     4     N    -25.1 -30.7 0.5                                           189                                                               AO.  AO.    235.5-   1     N    -19.2 -38.3 0.7                               A1   A      237                                                               AO.  AO.    235.5-   2     N    -19.7 -28.5 0.9                               A1   A      237                                                               AO   AO.    235.5-   4     N    -25.7 -29.0 1.7                               A1   A      237                                                               AO.  AO.    220-     1     N    -17.7 -44.7 1.0                               B1   B      221.5                                                             AO.  AO.    220-     2     N    -20.7 -32.8 1.5                               B1   B      221.5                                                             AO.  AO.    220-     4     N    -24.9 -28.3 1.5                               B1   B      221.5                                                             AO.  AO.    246-     1     N    -18.9 -28.4 1.4                               C1   C      249                                                               AO.  AO.    246-     2     N    -25.8 -26.9 0.8                               C1   C      249                                                               AO.  AO.    246-     4     N    -28.3 -23.1 0.8                               C1   C      249                                                               ______________________________________                                    

                  TABLE 5                                                         ______________________________________                                        Developer Using Modified Kynar Carrier                                                                                    T.O.                                          m.p.     Conc                   (mg                               Ex   CCA    (°C.)                                                                           (pph) P/S  2 min 10 min                                                                              admix)                            ______________________________________                                        AA2  AA     166.5-   1     N    -32.8 -71.8 0.2                                           171                                                               AA2  AA     166.5-   2     N    -39.8 -69.7 0.2                                           171                                                               AA2  AA     166.5-   4     N    -36.8 -54.2 0                                             171                                                               AB2  AB     260-     1     N    -29.4 -43.9 0.7                                           261.5                                                             AB2  AB     260-     2     N    -36.5 -32.4 1.1                                           261.5                                                             AB2  AB     260-     4     N    -35.3 -26.6 1.8                                           261.5                                                             AC2  AC     205-     1     N    -29.2 -65.5 0.0                                           208                                                               AC2  AC     205-     2     N    -37.1 -53.8 0.2                                           208                                                               AC2  AC     205-     4     N    -34.4 -34.5 0.9                                           208                                                               AD2  AD     256-     1     N    -25.8 -52.2 0                                             258                                                               AD2  AD     256-     2     N    -29.3 -40.8 0.3                                           258                                                               AD2  AD     256-     4     N    -36.1 -48.4 0.3                                           258                                                               AE2  AE     206-     1     N    -20.7 -63.2 0.3                                           212                                                               AE2  AE     206-     2     N    -31.2 -56.8 0.2                                           212                                                               AE2  AE     206-     4     N    -41.3 -32.1 0.7                                           212                                                               AF2  AF     222-     1     N    -25.2 -62.5 0.1                                           225.5                                                             AF2  AF     222-     2     N    -30.1 -43.6 0.2                                           225.5                                                             AF2  AF     222-     4     Y    -33.9 -28.7 2.8                                           225.5                                                             AG2  AG     267-     1     N    -29.5 -53.1 0.0                                           268.5                                                             AG2  AG     267-     2     N    -32.6 -33.6 0.8                                           268.5                                                             AG2  AG     267-     4     N    -33.6 -22.8 5.7                                           268.5                                                             AH2  AH     224-     1     N    -25.3 -59.7 0.1                                           227                                                               AH2  AH     224-     2     N    -33.4 -40.0 0.6                                           227                                                               AH2  AH     224-     4     N    -28.6 -23.8 2.0                                           227                                                               AI2  AI     216.5-   1     N    -20.0 -59.9 0.3                                           218.5                                                             AI2  AI     216.5-   2     N    -30.6 -42.5 0.6                                           218.5                                                             AI2  AI     216.5-   4     N    -34.6 -27.8 3.0                                           218.5                                                             AJ2  AJ     242-     1     N    - 13.9                                                                              -59.2 0.1                                           245                                                               AJ2  AJ     242-     2     N    -21.8 -46.6 0.4                                           245                                                               AJ2  AJ     242-     4     N    28.1  -33.3 1.0                                           245                                                               AK2  AK     192.5-   1     N    -33.3 -71.1 0.0                                           195                                                               AK2  AK     192.5-   2     N    -39.2 -60.2 0.1                                           195                                                               AK2  AK     192.5-   4     N    -38.0 -37.9 0.5                                           195                                                               AL2  AL     248.5-   1     N    -32.9 -64.6 0.2                                           249.5                                                             AL2  AL     248.5-   2     N    -36.3 -43.8 0.4                                           249.5                                                             AL2  AL     248.5-   4     N    -35.5 -27.9 1.1                                           249.5                                                             AM2  AM     245-     1     N    -21.4 -49.0 0.3                                           248                                                               AM2  AM     245-     2     N    -22.8 -33.1 0.3                                           248                                                               AM2  AM     245-     4     N    -28.0 -28.0 0.6                                           248                                                               AN2  AN     246-     1     N    -17.4 -50.3 0.2                                           248.5                                                             AN2  AN     246-     2     N    -24.0 -44.6 0.4                                           248.5                                                             AN2  AN     246-     4     N    -22.2 -28.8 0.9                                           248.5                                                             AO2  AO     186-     1     N    -6.5  -51.3 0.2                                           189                                                               AO2  AO     186-     2     N    -6.6  -52.8 0.1                                           189                                                               AO2  AO     186-     4     N    -13.0 -41.1 0.4                                           189                                                               AO.  AO.    235.5-   1     N    -23.3 -51.0 0.3                               A2   A      237                                                               AO.  AO.    235.5-   2     N    -20.9 -32.1 0.8                               A2   A      237                                                               AO.  AO.    235.5-   4     N    -28.3 -26.6 2.6                               A2   A      237                                                               AO.  AO.    220-     1     N    -21.9 -61.0 0.3                               B2   B      221.5                                                             AO.  AO.    220-     2     N    -18.6 -36.2 0.4                               B2   B      221.5                                                             AO.  AO.    220-     4     N    -22.9 -25.7 1.2                               B2   B      221.5                                                             AO.  AO.    246-     1     N    -14.1 -44.3 0.2                               C2   C      249                                                               AO.  AO.    246-     2     N    -20.1 -40.0 0.3                               C2   C      249                                                               AO.  AO.    246-     4     N    -30.6 -40.7 0.7                               C2   C      249                                                               ______________________________________                                    

EXAMPLES AP1,AP2

Sulfonamide charge control agent having the structural formula:##STR41## was prepared as follows.

The sulfonamide of Examples T1-T2 (40.80 grams, 0.10 mol) was admixedwith 4.2 grams (0,105 mol) of NaOH and 1 liter of water. The reactionmixture was heated to boiling, with stirring, refluxed for 20 minutesand cooled. Precipitate was collected, washed with water and dried. Thesolid was extracted with 400 ml of methanol and insoluble material wasfiltered off. The filtrate was concentrated and dried, thenrecrystallized from methyl ethyl ketone (filtered hot through supercel).Yield was 14.1 grams (32.8%). Melting point was 345-347° C. Elementalanalysis found C=58.44, H=5.78, N=3.37, Cl=8.52, S=6.22, Na=5.1. Thiscompares to calculated values for C₂₁ H₂₅ ClNNaO₃ S of C=58.67, H=5.86,N=3.26, Cl=8.25, S=7.46, Na=5.35. An NMR spectrum was obtained indeuterated dimethylsulfoxide, which agreed with the structure of theexpected product.

The same procedures were substantially followed in the preparation oftoners and developers and in evaluating materials as described inExamples A, except that only colorless toners were produced. Results arepresented in Tables 6-7.

EXAMPLES AQ1,AQ2

Sulfonamide charge control agent having the structural formula:##STR42## was prepared as follows.

A mixture of 2.61 grams (0.01 mol) of N-benzoylbenzenesulfonamide, 0.84grams (0.01 mol) NaHCO₃ in about 50 ml of water, was prepared andstirred with warming. Foaming was observed. The reaction mixture wasfiltered and the filtrate was concentrated to dryness. Yield was 2.06grams (79.25%). Melting point was in excess of 250° C. Elementalanalysis found C=54.72, H=3.59, N=5.06, S=11.24, Na=7.9. This comparesto calculated values for C₁₃ H₁₀ NO₃ SNa of C=55.12, H=3.56, N=4.94,S=11.32, Na=8.12. An NMR spectrum, in D₂ O, was obtained which agreedwith the structure of the expected product.

The same procedures were substantially followed in the preparation oftoners and developers and in evaluating materials as described inExamples A, except that only colorless toners were produced. Results arepresented in Tables 6-7.

EXAMPLES AR1,AR2

Sulfonamide charge control agent having the structural formula:##STR43## was prepared as follows.

The sulfonamide of Examples Z1-Z2 (26.13 grams, 0.10 mol), MgCO₃ (4.22grams, 0.05 mol) and 375 ml of water were placed in a flask and heatedwith stirring for 3 hours; at which time the reaction mixture was aclear, light yellow. The reaction mixture was cooled in an ice bath anda fluffy white precipitate formed. The solid was filtered out and thesolution rotary evaporated providing a hard white solid. Yield was 20.14grams (73.9%). Melting point was in excess of 400° C. Elemental analysisfound C=57.00, H=3.77, N=5.27, S=11.09, Mg=4.1. This compares tocalculated values for (C₁₃ H₁₀ NO₃ S)₂ Mg of C=57.31, H=3.70, N=5.14,S=11.77, Mg=4.46.

The same procedures were substantially followed in the preparation oftoners and developers and in evaluating materials as described inExamples A, except that only colorless toners were produced.

                  TABLE 6                                                         ______________________________________                                        Developer Using PMMA Coated Carrier                                                                           Q/m    Q/m   T.O.                                          m.p.   Conc        (μc/g)                                                                            (μc/g)                                                                           (mg                              Ex   CCA     (°C.)                                                                         (pph)  P/S  2 min  10 min                                                                              admix)                           ______________________________________                                        AP1  AP      345-   1      Y    -25.0  -21.9 3.3                                           347                                                              AP1  AP      345-   2      Y    -24.4  -20.0 1.6                                           347                                                              AP1  AP      345-   4      Y    -19.0  -17.6 1.8                                           347                                                              AQ1  AQ      --     1      Y    -14.6  -19.3 8.5                              AQ1  AQ      --     2      Y    -16.6  -20.1 23.2                             AQ1  AQ      --     4      Y    -16.7  -15.5 22.4                             AR1  AR      --     1      Y    -21.4  -31.2 8.0                              AR1  AR      --     2      Y    -23.6  -24.5 11.3                             AR1  AR      --     4      Y    -24.2  -21.6 17.1                             ______________________________________                                    

                  TABLE 7                                                         ______________________________________                                        Developer Using Modified Kynar Carrier                                                                                     T.O.                                          m.p.   Conc                     (mg                              Ex   CCA     (°C.)                                                                         (pph)  P/S  2 min  10 min                                                                              admix)                           ______________________________________                                        AP2  AP      345-   1      Y    -6.8   -32.6 1.5                                           347                                                              AP2  AP      345-   2      Y    -6.7   -32.6 1.2                                           347                                                              AP2  AP      345-   4      Y    -7.3   -30.0 1.4                                           347                                                              AQ2  AQ      --     1      Y    -1.9   -27.7 6.2                              AQ2  AQ      --     2      Y    -1.4   -14.4 26.0                             AQ2  AQ      --     4      Y    POS     -7.4 --                               AR2  AR      --     1      Y    -6.3   -45.9 2.0                              AR2  AR      --     2      Y    -4.0   -26.1 2.0                              AR2  AR      --     4      Y    -6.7   -22.7 5.5                              ______________________________________                                    

EXAMPLES AS1,AS2

Sulfonamide charge control agent having the structural formula:##STR44## was prepared as follows.

N-Methyl-4-chlorobenzenesulfonamide (20.57 grams, 0.10 mol) and3,5-di-t-butyl-4-hydroxybenzoyl chloride (26.87 grams, 0.10 mol) wereadmixed with toluene (200 ml) in a flask and refluxed for 18.5 hours.The reaction mixture was poured into 600 ml ligroine (bp =35-60° C.). Awhite solid crystallized, was collected, washed with more ligroine,dried, recrystallized from CH₃ CN, collected and dried. Yield was 20.1grams (45.89%). Melting point was 169-172° C. Elemental analysis foundC=60.17, H=6.19, N=3.36, Cl=8.22, S=8.24. This compares to calculatedvalues for C₂₂ H₂₈ ClNO₄ S of C=60.33, H=6.44, N=3.20, Cl=8.09, S=7.32.An NMR spectrum, in deuterated chloroform, was obtained which agreedwith the structure of the expected product.

The same procedures were substantially followed in the preparation oftoners and developers and in evaluating materials as described inExamples A, except that only colorless toners were produced. Results arepresented in Tables 8-9.

EXAMPLES AT1,AT2-AU1,AU2

The same procedures were substantially followed as described in ExamplesAS1-AS2, except that starting materials in the aroylsulfonamidepreparation were different. Results are presented in Tables 8-9.Sulfonamides utilized in the examples are indicated by the designationson the following structural formulas: ##STR45##

                  TABLE 8                                                         ______________________________________                                        Developer Using PMMA Coated Carrier                                                                                        T.O.                                          m.p.   Conc                     (mg                              Ex   CCA     (°C.)                                                                         (pph)  P/S  2 min  10 min                                                                              admix)                           ______________________________________                                        AS1  AS      169-   1      N    -16.0  -42.8 1.9                                           172                                                              AS1  AS      169-   2      N    -16.5  -43.6 2.9                                           172                                                              AS1  AS      169-   4      N    -16.0  -44.5 4.4                                           172                                                              AT1  AT      152.5- 1      N    -15.8  -48.2 2.5                                           155                                                              AT1  AT      152.5- 2      N    -13.9  -51.3 3.9                                           155                                                              AT1  AT      152.5- 4      N    -16.0  -49.8 3.6                                           155                                                              AU1  AU      187-   1      Y    -14.5  -46.0 5.0                                           188                                                              AU1  AU      187-   2      Y    -15.6  -48.3 6.7                                           188                                                              AU1  AU      187-   4      Y    -15.8  -50.8 6.7                                           188                                                              ______________________________________                                    

                  TABLE 9                                                         ______________________________________                                        Developer Using Modified Kynar Carrier                                                                                     T.O.                                          m.p.   Conc                     (mg                              Ex   CCA     (°C.)                                                                         (pph)  P/S  2 min  10 min                                                                              admix)                           ______________________________________                                        AS2  AS      169-   1      N    -4.8   -58.6 0.6                                           172                                                              AS2  AS      169-   2      N    -3.5   -54.2 0.3                                           172                                                              AS2  AS      169-   4      N    -3.5   -59.7 0.5                                           172                                                              AT2  AT      152.5- 1      N    -10.2  -73.7 0.2                                           155                                                              AT2  AT      152.5- 2      N    -6.4   -67.3 0.2                                           155                                                              AT2  AT      152.5- 4      N    -7.2   -68.2 0.3                                           155                                                              AU2  AU      187-   1      Y    -13.8  -63.7 0                                             188                                                              AU2  AU      187-   2      Y    -13.4  -64.6 0                                             188                                                              AU2  AU      187-   4      Y    -13.6  -71.7 0.1                                           188                                                              ______________________________________                                    

EXAMPLES AV1,AV2

Sulfonamide charge control agent having the structural formula:##STR46## was prepared as follows.

To a solution of N-(phenylsulfonyl)benzenecarboximidoyl chloride (8.39grams, 0.03 mol) in dichloromethane (50 ml) was added concentrated NH₄OH (50 ml). The reaction mixture was stirred for about 10 minutes whilean exothermic reaction occurred. The reaction mixture was then heated ona steam bath to drive off CH₂ Cl₂. A solid crystallized, was collected,washed with water, recrystallized from methanol and dried in a vacuumoven. Yield was 5.9 grams (75.5%). Melting point was 150-152° C.Elemental analysis found C=60.01, H=4.63, N=10.63, S=12.10. Thiscompares to calculated values for C₁₃ H₁₂ N₂ O₂ S of C=59.98, H=4.65,N=10.76, S=12.32. An NMR spectrum was obtained in deuterateddimethylsulfoxide, which agreed with the structure of the expectedproduct.

The same procedures were substantially followed in the preparation oftoners and developers and in evaluating materials as described inExamples A, except that only colorless toners were produced. Results arepresented in Tables 10-11.

EXAMPLES AX1,AX2-BA1,BA2

In AX1,AX2; AY1,AY2; and BA1,BA2; the same procedures were substantiallyfollowed as described in Examples AV1-AV2, except that startingmaterials in the aroylsulfonamide preparation were different. ExamplesAZ1,AZ2 were prepared from benzamidine·HCl and paratoluene sulfonylchloride in accord with a general procedure described in Journal of theAmerican Chemical Society, Vol. 64, (1942) p. 2763 and following a morespecific procedure reported in Zh. Org. Khim., Vol 11, No. 1, (1975) p.113. Results are presented in Tables 10-11.

Sulfonamides utilized in these examples are indicated by thedesignations on the following structural formulas: ##STR47##

                  TABLE 10                                                        ______________________________________                                        Developer Using PMMA Coated Carrier                                                                                        T.O.                                          m.p.   Conc                     (mg                              Ex   CCA     (°C.)                                                                         (pph)  P/S  2 min  10 min                                                                              admix)                           ______________________________________                                        AV1  AV      150-   1      N     -8.5  -36.5 13.0                                          152                                                              AV1  AV      150-   2      N    -12.9  -46.7 7.0                                           152                                                              AV1  AV      150-   4      N    -15.0  -43.8 8.2                                           152                                                              AX1  AX      239-   1      N    -14.8  -42.3 1.8                                           240.5                                                            AX1  AX      239-   2      N    -21.4  -38.5 1.1                                           240.5                                                            AX1  AX      239-   4      N    -26.1  -33.0 0.8                                           240.5                                                            AY1  AY      184-   1      N    -12.4  -47.3 6.2                                           185                                                              AY1  AY      184-   2      N    -10.7  -46.1 3.2                                           185                                                              AY1  AY      184-   4      Y    -11.2  -46.8 4.3                                           185                                                              AZ1  AZ      156-   1      N    -14.5  -36.3 4.7                                           158                                                              AZ1  AZ      156-   2      N    -16.0  -32.2 1.4                                           158                                                              AZ1  AZ      156-   4      N    -16.5  -28.8 2.7                                           158                                                              BA1  BA      159-   1      N    -13.1  -50.9 5.9                                           161                                                              BA1  BA      159-   2      N    -13.2  -47.5 4.8                                           161                                                              BA1  BA      159-   4      N    -14.9  -47.9 3.4                                           161                                                              ______________________________________                                    

                  TABLE 11                                                        ______________________________________                                        Developer Using Modified Kynar Carrier                                                                                     T.O.                                          m.p.   Conc                     (mg                              Ex   CCA     (°C.)                                                                         (pph)  P/S  2 min  10 min                                                                              admix)                           ______________________________________                                        AV2  AV      150-   1      N    -14.8  -68.5 0.1                                           152                                                              AV2  AV      150-   2      N    -17.6  -69.5 0.2                                           152                                                              AV2  AV      150-   4      N    -16.0  -60.1 0.2                                           152                                                              AX2  JAX     239-   1      N    -13.4  -60.6 0.3                                           240.5                                                            AX2  AX      239-   2      N    -22.8  -64.7 0.3                                           240.5                                                            AX2  AX      239-   4      N    -30.7  -58.1 0.3                                           240.5                                                            AY2  AY      184-   1      N    -16.0  -69.2 0.2                                           185                                                              AY2  AY      184-   2      N    -14.2  -69.0 0.4                                           185                                                              AY2  AY      184-   4      Y    -11.6  -74.2 0.4                                           185                                                              AZ2  AZ      156-   1      N    -13.2  -54.2 0.4                                           158                                                              AZ2  AZ      156-   2      N    -12.0  -53.4 0.3                                           158                                                              AZ2  AZ      156-   4      N    -11.4  -40.2 0.2                                           158                                                              BA2  BA      159-   1      N    -10.5  -76.8 0.0                                           161                                                              BA2  BA      159-   2      N     -8.3  -88.5 0.2                                           161                                                              BA2  BA      159-   4      N    -10.6   81.3 0.0                                           161                                                              ______________________________________                                    

EXAMPLES BB1,BB2

Sulfonamide charge control agent having the structural formula:##STR48## was prepared as follows.

N-(4-Chlorobenzenesulfonyl)-3,5-di-t-butylbenzenecarboximoyl chloridewas first prepared in accordance with the following procedure:

A mixture of 30.5 grams (0.075 mol) ofN-(3,5-di-t-butylbenzoyl)-4-chlorobenzene-sulfonamide and 17.13 grams(0.082 mol) PCl₅ was heated in a 170° C. bath with stirring for 3 hours.The reaction mixture was then concentrated on a steam bath under vacuum.Heptane was added to bring the total volume of the reaction mixture to200 ml. The reaction mixture was filtered through supercel and cooled ina dry ice/isopropanol bath. A white solid crystallized, was collected,washed with Ligroine (bp =35°-60° C.) and dried. Yield was 17.14 grams(53.6%). Melting point was 91°-92.5° C. Elemental analysis foundC=58.78, H=5.81, N=3.12, Cl=16.16, S=7.77. This compares to calculatedvalues for C₂₁ H₂₅ Cl₂ NO₂ S of C=59.15, H=5.91, N=3.28, Cl=16.63,S=7.52. An NMR spectrum was obtained in deuterated chloroform, whichagreed with the structure of the expected product.

To a solution of 21.62 grams (0.09 mol) of Na₂ S·9H₂ O in 150 ml ofwater, was added in a stream over about 2 minutes, a solution of 31.98grams (0.075) ofN-(4-chlorobenzenesulfonyl)-3,5-di-t-butylbenzenecarboximoyl chloride in150 ml of tetrahydrofuran. A mildly exothermic reaction occurred and thereaction mixture became green-yellow. The reaction mixture was stirredfor about 2 hours then acidified with concentrated HCl (12 ml). Thereaction mixture became bright orange and organic and aqueous layersseparated. The organic layer was separated, washed with water anddichloromethane was added. The organic layer was separated, dried overMgSO₄ and concentrated as an orange-yellow solid residue. The residuewas recrystallized from 240 ml of 3:1 heptane:toluene. Yellow needleswere collected, washed with Ligroine (bp=35°-60° C.) and dried. Yieldwas 22.9 grams (72.0%). Melting point was 177°-179° C. Elementalanalysis found C=59.37, H=6.24, N=3.26, Cl=8.43, S=14.98. This comparesto calculated values for C₂₁ H₂₆ ClNO₂ S₂ of C=59.49, H=6.18, N=3.30,Cl=8.36, S=15.12. An NMR spectrum was obtained in which agreed with thestructure of the expected product.

The same procedures were substantially followed in the preparation oftoners and developers and in evaluating materials as described inExamples A, except that only colorless toners were produced. Results arepresented in Tables 12-13.

EXAMPLES BC1,BC2

The same procedures were substantially followed as described in ExamplesBB, except that starting materials in the carbonothionylsulfonamidepreparation were different. Results are presented in Tables 12-13. Thestructural formula of the sulfonamides utilized in Examples BC is:##STR49##

                  TABLE 12                                                        ______________________________________                                        Developer Using PMMA Coated Carrier                                                                                        T.O.                                          m.p.   Conc                     (mg                              Ex   CCA     (°C.)                                                                         (pph)  P/S  2 min  10 min                                                                              admix)                           ______________________________________                                        BB1  BB      177-   1      N    -16.8  -49.8 1.5                                           179                                                              BB1  BB      177-   2      N    -20.9  -49.2 2.1                                           179                                                              BB1  BB      177-   4      N    -23.9  -44.3 3.2                                           179                                                              BC1  BC      140-   1      N    -22.4  -49.1 1.5                                           142                                                              BC1  BC      140-   2      N    -19.0  -37.9 1.8                                           142                                                              BC1  BC      140-   4      N    -29.4  -36.6 6.3                                           142                                                              ______________________________________                                    

                  TABLE 13                                                        ______________________________________                                        Developer Using Modified Kynar Carrier                                                                                     T.O.                                          m.p.   Conc                     (mg                              Ex   CCA     (°C.)                                                                         (pph)  P/S  2 min  10 min                                                                              admix)                           ______________________________________                                        BB2  BB      177-   1      N    -13.7  -66.8 0.3                                           179                                                              BB2  BB      177-   2      N    -17.6  -62.4 0.3                                           179                                                              BB2  BB      177-   4      N    -27.9  -57.8 0.3                                           179                                                              BC2  BC      140-   1      N    -25.9  -64.4 0.2                                           142                                                              BC2  BC      140-   2      N    -23.7  -58.5 0.0                                           142                                                              BC2  BC      140-   4      N    -41.2  -57.6 0.0                                           142                                                              ______________________________________                                    

EXAMPLES BG1,BG2

Sulfonamide charge control agent having the structural formula:##STR50## was prepared as follows.

A mixture of 24.1 grams (0.20 mol) of pivaloyl chloride, 19.02 grams(0.20 mol) of methanesulfonamide, and 31.64 grams (0.40 mol) of pyridinewas heated on a steam bath for 1.5 hours. The reaction mixture was thentaken up in CH₂ Cl₂, washed twice with dilute HCl, washed once withwater, dried over MgSO₄, concentrated, recrystallized from toluene,collected, washed with Ligroine (bp=35°-60° C.) and dried. Yield was17.7 grams (49.38%). Melting point=128°-129.5° C. Elemental analysisfound C=40.31, H=7.20, N=7.91, S=18.20. This compares to calculatedvalues for C₆ H₁₃ NO₃ S of C=40.21, H=7.31, N=7.81, S=17.89. An NMRspectrum was obtained in which agreed with the structure of the expectedproduct.

The same procedures were substantially followed in the preparation oftoners and developers and in evaluating materials as described inExamples A, except that only colorless toners were produced. Results arepresented in Tables 16-17.

EXAMPLES BH1,BH2

The same procedures were substantially followed as described in ExamplesBG, except that starting materials in the aroylsulfonamide preparationwere different. Results are presented in Tables 16-17. Sulfonamidesutilized in the examples are indicated by the designations on thefollowing structural formulas: ##STR51##

                  TABLE 16                                                        ______________________________________                                        Developer Using PMMA Coated Carrier                                                                                        T.O.                                          m.p.   Conc                     (mg                              Ex   CCA     (°C.)                                                                         (pph)  P/S  2 min  10 min                                                                              admix)                           ______________________________________                                        BG1  BG      128-   1      N    -12.0  -21.4 3.2                                           129.5                                                            BG1  BG      128-   2      N    -11.7  -19.7 4.6                                           129.5                                                            BG1  BG      128-   4      N    -11.5  -17.7 4.3                                           129.5                                                            BH1  BH      207-   1      N    -15.3  -32.8 1.2                                           209                                                              BH1  BH      207-   2      N    -16.0  -32.8 1.8                                           209                                                              BH1  BH      207-   4      N    -23.8  -38.2 1.1                                           209                                                              ______________________________________                                    

                  TABLE 17                                                        ______________________________________                                        Developer Using Modified Kynar Carrier                                                                                     T.O.                                          m.p.   Conc                     (mg                              Ex   CCA     (°C.)                                                                         (pph)  P/S  2 min  10 min                                                                              admix)                           ______________________________________                                        BG2  BG      128-   1      N     -1.5  -46.5 0.6                                           129.5                                                            BG2  BG      128-   2      N     -1.7  -40.0 0.7                                           129.5                                                            BG2  BG      128-   4      N     -1.6  -29.4 1.0                                           129.5                                                            BH2  BH      207-   1      N    -10.2  -49.5 0.3                                           209                                                              BH2  BH      207-   2      N     -9.5  -45.7 0.3                                           209                                                              BH2  BH      207-   4      N    -15.1  -37.0 0.5                                           209                                                              ______________________________________                                    

COMPARATIVE EXAMPLES COMPARATIVE EXAMPLES 1a,1b

Toners and developers were prepared and evaluated in the same manner asin Examples A1-A2, with the exception that no charge control agent wasused.

COMPARATIVE EXAMPLES 2a,2b

Saccharin (ortho-benzoic sulfimide), which has the structural formula:##STR52## was purchased from Aldrich Chemical Company of Milwaukee, Wis.Toners and developers were prepared and evaluated in the same manner asin Examples A, with the exception that saccharin was used in place ofsulfonamide charge control agent. Results are presented in Tables 18-19.

COMPARATIVE EXAMPLES 3a, 3b

1-(2-Hydroxyphenyl)-3-(3,5-di-t-butylphenyl)-1,3-propanedione, which hasthe structural formula: ##STR53## was prepared utilizing the followingreaction scheme: ##STR54##

A mixture of 2'-(3,5-di-t-butylbenzoyloxy)acetophenone (55.0 g, 0.156mol), K₂ CO₃ (165 g), and toluene (550 ml) was prepared and heated on asteam bath with stirring. Within about two hours, a considerable amountof yellow solid had formed. The heating was continued for a total ofabout 21 hours. The reaction mixture was filtered hot. The solidcollected was washed with ligroine (bp=35°-60° C.), dried, slurried inwater, collected, and washed with a 1:1 mixture of acetic acid andwater. The solid became taffy-like. The aqueous phase was decanted andthe product was washed with water, and recrystallized in about 300 ml ofethanol. Solid in the form of yellow needles was collected and dried.The solid was then dissolved in dichloromethane and the solution wasfiltered to remove water soluble salts. The filtrate was washed withwater, dried over MgSO₄ and concentrated. Oily residue was obtainedwhich crystallized on cooling. This solid was recrystallized from 50 mlof ethanol. The precipitate was collected and dried. Yield was 20.3grams (36.9%). Melting point was 92°-94° C. (Began to melt at 75° C.then solidified. Completely melted at 92°-94° C.). Elemental analysisfound C=78.37, H=7.93. This compares to calculated values for C₂₂ H₂₈ O₃of C=78.38, H=8.01. An NMR spectrum, in deuterated chloroform, wasobtained which agreed with the structure of the expected product.

Toners and developers were prepared and evaluated in the same manner asin Examples A1,A2, with the exception that1-(2-hydroxyphenyl)-3-(3,5-di-t-butylphenyl)-1,3-propanedione was usedin place of sulfonamide charge control agent. Results are reported inTables 18-19.

COMPARATIVE EXAMPLES 4a,4b

Bis{1-(2-hydroxyphenyl)-3-(4-t-butylphenyl)-1,3-propanedionato)zinc,which has the structural formula: ##STR55## was prepared utilizing thefollowing reaction scheme: ##STR56##1-(2-hydroxyphenyl)-3-(4-t-butylphenyl)-1,3-propanedione was prepared bythe procedure described in Comparative Examples 4, with the exceptionthat 2'-(4-t-butylbenzoyloxy)acetophenone was substituted for2'-(3,5-di-t-butylbenzoyloxy)acetophenone.

A solution of 1-(2-hydroxyphenyl)-3-(4-t-butylphenyl)- 1,3-propanedione(2.96 g, 0.01 mol) in methanol (50 ml) was prepared with heating. Tothis solution, was added a solution of zinc acetate dihydrate (1.11 g, 5mmol) in methanol (10 ml), which had been preheated. The resultingreaction mixture was heated on a steam bath for 15 minutes. A solidcrystalline precipitate that formed was filtered hot, washed withmethanol and dried. Yield was 1.17 grams. Melting point was 126-128° C.(The melt recrystallized to provide a product with a melting point inexcess of 250° C). Elemental analysis found C=69.19, H=5.68, Zn=11.6.This compares to calculated values for C₃₈ H₃₈ O₆ Zn of C=69.57, H=5.84,Zn=9.97. An NMR spectrum, in deuterated chloroform, was obtained whichagreed with the structure of the expected product.

Toners and developers were prepared and evaluated in the same manner asin Examples A1,A2, with the exception thatBis{1-(2-hydroxyphenyl)-3-(4-t-butylphenyl)-1,3-propanedionato}zinc wasused in place of sulfonamide charge control agent. Results are reportedin Tables 18-19.

COMPARATIVE EXAMPLES 5a,5b

3,5-Di-t-butyl-4-hydroxybenzenesulfonamide has the structural formula##STR57## and was prepared as follows.

3,5-Di-t-butyl-4-hydroxybenzenesulfonyl chloride was prepared accordingto the procedure of U.S. Pat. No. 5,157,156 to Giodana et al.

A solution of 149.5 grams (0.49 mol) of3,5-di-t-butyl-4-hydroxybenzenesulfonyl chloride in 1700 ml of methylenechloride was treated with ammonia for 35 minutes. The milky organiclayer was concentrated to dryness and the solid residue was taken up inacetone, filtered and concentrated. The residue was taken up in ether,washed with water and dried over MgSO₄ and concentrated. The residue wasrecrystallized from 600 ml of isopropanol to give 99.0 grams of product(70.8% of theory). Melting point=166-168° C. Elemental analysis foundC=58.55, H=8.07, N=4.98, S=10.93. This compares to calculated values forC₁₄ H₂₃ NO₃ S of C=58.92, H=8.12, N=4.91, S=11.23. An NMR spectrum wasobtained which agreed with the structure of the expected product.

Toners and developers were prepared and evaluated in the same manner asin Examples B, with the exception of the different charge control agent.Results are reported in Tables 18-19.

                  TABLE 18                                                        ______________________________________                                        Developer Using PMMA Coated Carrier                                                                                     T.O.                                Com    m.p.    Conc                       (mg                                 Ex     (°C.)                                                                          wgt %    P/S  2 min  10 min                                                                              admix)                              ______________________________________                                        1a     --      --       --    -7.8  -49.8 4.7                                 2a     228     1        N    -16.4  -28.1 24.6                                2a     228     2        N    -18.8  -30.4 13.5                                2a     228     4        N    -28.1  -36.6 5.0                                 3a     92-94   1        N    -10.8  -37.3 1.8                                 3a     92-94   2        N    -11.0  -35.4 2.1                                 3a     92-94   4        N    -11.7  -34.1 2.8                                 4a     126-    1        Y    -15.5  -35.1 1.5                                        128                                                                    4a     126-    2        Y    -15.2  -34.1 3.9                                        128                                                                    4a     126-    4        Y    -15.2  -33.7 2.8                                        128                                                                    5a     166-    1        N    -16.7  -44.5 0.8                                        168                                                                    5a     166-    2        N    -17.4  -47.1 3.1                                        168                                                                    5a     166-    4        N    -17.8  -48.9 2.2                                        168                                                                    ______________________________________                                    

                  TABLE 19                                                        ______________________________________                                        Developer Using modified Kynar Carrier                                                                                  T.O.                                Com    m.p.    Conc                       (mg                                 Ex     (°C.)                                                                          wgt %    P/S  2 min  10 min                                                                              admix)                              ______________________________________                                        1b     --      --       --    -7.3  -73.2 0.1                                 2b     228     1        N    bich   -29.7 11.2                                2b     228     2        N    bich    -4.7 126.3                               2b     228     4        N    bich    -1.8 217.8                               3b     92-94   1        N     -2.2  -53.0 0.3                                 3b     92-94   2        N     -1.7  -43.6 0.0                                 3b     92-94   4        N     -1.9  -40.2 0.4                                 4b     126-    1        Y     -7.3  -46.7 0.3                                        128                                                                    4b     126-    2        Y     -3.6  -36.9 0.6                                        128                                                                    4b     126-    4        Y     -4.4  -38.7 0.5                                        128                                                                    5b     166-    1        N    -13.7  -73.2 0.1                                        168                                                                    5b     166-    2        N    -12.5  -65.3 0.2                                        168                                                                    5b     166-    4        N    -10.4  -70.6 0.2                                        168                                                                    ______________________________________                                    

While specific embodiments of the invention have been shown anddescribed herein for purposes of illustration, the protection affordedby any patent which may issue upon this application is not strictlylimited to a disclosed embodiment; but rather extends to allmodifications and arrangements which fall fairly within the scope of theclaims which are appended hereto:

What is claimed is:
 1. An electrophotographic toner comprisingthermoplastic polymeric binder and a charge control agent, saidpolymeric binder forming a matrix phase, said charge control agent beingselected from the group consisting of sulfonamides having the generalstructure: ##STR58## and metal salts thereof; whereinT¹ is independentlyselected from the group consisting of: H, alkyl having from 1 to 20carbons, cycloalkyl having from 3 to 18 carbons, and aromatic andheteroaromatic ring systems having a solitary ring or 2 to 3 linked orfused rings; R¹ is O, S, N--H, N--R⁵, or N--L--R⁵, wherein L is alinking group selected from; ##STR59## and R⁵ is independently selectedfrom the group consisting of alkyl having from 1 to 20 carbons,cycloalkyl having from 3 to 18 carbons, and aromatic and heteroaromaticring systems having a solitary ring or 2 to 3 linked or fused rings; L¹and L² are each independently a direct link or divalent alkyl orfluoroalkyl having from 1 to 20 carbons; and R^(a) and R^(b) are eachindependently selected from the group consisting of H, F and ringsystems having a solitary ring or from 2 to 3 fused or linked rings,said ring system being substituted or unsubstituted, said ring systemhaving from 3 to 34 carbons, including carbons of substituents; with theprovisos that if L¹ is a direct link, R^(a) is a ring system and if L²is a direct link, R^(b) is a ring system.
 2. A toner according to claim1 wherein said charge control agent has the general structure: ##STR60##wherein M is a metal ion, ande is the valence of M.
 3. A toner accordingto claim 1 wherein T¹ is H.
 4. A toner according to claim 3 wherein saidsulfonamide has the general structure ##STR61## wherein T² is --H, --R⁵,or --L--R⁵.
 5. A toner according to claim 3 wherein R^(a) and R^(b) areselected from the group consisting of H and F.
 6. A toner according toclaim 3 wherein one of R^(a) and R^(b) is H and other of R^(a) and R^(b)is a ring system.
 7. A toner according to claim 3 wherein saidsulfonamide has the general structure ##STR62## wherein R¹ is O or S;L¹and L² are each independently a direct link or divalent alkyl orfluoroalkyl having from 1 to 20 carbons; R^(a) and R^(b) are each a ringsystem having a single ring or from 2 to 3 fused or linked rings, saidring system having from 3 to 34 carbons, including substituent carbons.8. A toner according to claim 7 wherein at least one of R^(a) and R^(b)is substituted by a moiety selected from the group consisting of: H,alkyl having from 1 to 20 carbons, NO₂, NH₂, OH, COOH, cycloalkyl havingfrom 3 to 6 carbons, halo, alkycarbonyloxy having from 2 to 20 carbonsor carboalkoxy having from 2 to 20 carbons, and alkoxy having from 1 to20 carbons.
 9. A toner according to claim 7 wherein R¹ is O.
 10. A toneraccording to claim 9 wherein at least one of R^(a) and R^(b) issubstituted by tertiary alkyl having from 4 to 20 carbons.
 11. A toneraccording to claim 9 wherein L¹ is a direct link.
 12. A toner accordingto claim 11 wherein at least one of R^(a) and R^(b) is substituted bytertiary butyl.
 13. A toner according to claim 12 wherein L² is a directlink.
 14. A toner according to claim 9 wherein said charge control agentis selected from the group consisting of: ##STR63##
 15. A toneraccording to claim 7 wherein one of R^(a) and R^(b) is substituted by atleast one electron withdrawing group and the other one of R^(a) andR^(b) is substituted by at least one tertiary alkyl having from 4 to 20carbons, with the proviso that the number of electron withdrawing groupsis equal to or less than the number of t-alkyls.
 16. A toner accordingto claim 15 wherein R¹ is O.
 17. A toner according to claim 16 whereinone of R^(a) and R^(b) is substituted by at least one electronwithdrawing group and the other one of R^(a) and R^(b) is substituted byat least one tertiary butyl.
 18. A toner according to claim 16 whereinL¹ and L² are direct links, and R^(a) and R^(b) are phenyl.
 19. A toneraccording to claim 16 wherein said sulfonamide is selected from thegroup consisting of: ##STR64##
 20. A toner according to claim 7 whereinat least one of R^(a) and R^(b) is phenyl having two t-butylsubstituents and a third substituent selected from the group consistingof NO₂, OH, NH₂, N(CHB)₂, alkyl having from 1 to 8 carbons, and alkoxyhaving from 1 to 8 carbons.
 21. A toner according to claim 7 wherein atleast one of R^(a) and R^(b) is ##STR65## where T is tert-alkyl havingfrom 4 to 8 carbons.
 22. A toner according to claim 7 wherein at leastone of R^(a) and R^(b) includes the moiety: ##STR66## wherein T istertiary alkyl having from 4 to 8 carbons.
 23. A toner according toclaim 7 wherein at least one of R^(a) and R^(b) includes the moiety:##STR67## wherein T is tertiary alkyl having from 4 to 8 carbons; andRis selected from the group consisting of OH, NH₂, N(CH₃)₂, alkyl havingfrom 1 to 8 carbons, and alkoxy having from 1 to 8 carbons.
 24. A toneraccording to claim 23 wherein R¹ is O.
 25. A toner according to claim 23wherein R is OH.
 26. A toner according to claim 23 wherein one of R^(a)and R^(b) has the general structure: ##STR68## and the other has thesame general structure or is a ring system having a single ring or from2 to 3 fused or linked rings, said ring system having from 6 to 14carbons and at least one substituent selected from the group consistingof alkyl having from 1 to 20 carbons, NO₂, NH₂, OH, COOH, cycloalkylhaving from 3 to 6 carbons, halo, alkycarbonyloxy having from 2 to 20carbons or carboalkoxy having from 2 to 20 carbons, and alkoxy havingfrom 1 to 20 carbons.
 27. A toner according to claim 23 wherein saidsulfonamide has the general structure: ##STR69##
 28. A toner accordingto claim 23 wherein L¹ and L² are direct links and both R^(a) and R^(b)comprise substituted phenyl moieties.
 29. A toner according to claim 23wherein said charge control agent is selected from the group consistingof: ##STR70##
 30. A toner according to claim 23 wherein said binder isselected from the group consisting of: styrene-butyl-acrylate copolymer.31. An electrostatographic developer according to claim 1 wherein saidcarrier particles comprise core material coated with fluorohydrocarbonpolymer or poly(methyl methacrylate).
 32. A method for developing latentimages comprising forming an electrostatic latent image with a developercomprised of carrier particles and the toner defined by claim 1,followed by transferring the image to a suitable substrate andpermanently affixing the image thereto.
 33. A toner according to claim 1whereinR^(a) is selected from the group consisting of H, F and ringsystems having a solitary ring or from 2 to 3 fused or linked rings,said ring system being substituted or unsubstituted, said ring systemhaving from 3 to 34 carbons, including carbons of substituents; andR^(b) is independently selected from the group consisting of H, F andaryl ring systems having a solitary ring or from 2 to 3 fused or linkedrings, said ring system being substituted or unsubstituted, said ringsystem having from 3 to 34 carbons, including carbons of substituents.34. An electrostatographic developer including toner and carrierparticles, said toner comprising polymeric binder and a charge controlagent selected from the group consisting of sulfonamides having thegeneral structure: ##STR71## and metal salts thereof; whereinT¹ isindependently selected from the group consisting of: H, alkyl havingfrom 1 to 20 carbons, cycloalkyl having from 3 to 18 carbons, andaromatic and heteroaromatic ring systems having a solitary ring or 2 to3 linked or fused rings; R¹ is O, S, N--H, N--R⁵, or N--L--R⁵, wherein Lis a linking group selected from: ##STR72## and R⁵ is independentlyselected from the group consisting of alkyl having from 1 to 20 carbons,cycloalkyl having from 3 to 18 carbons, and aromatic and heteroaromaticring systems having a solitary ring or 2 to 3 linked or fused rings; L¹and L² are each independently a direct link or divalent alkyl orfluoroalkyl having from 1 to 20 carbons; and R^(a) and R^(b) are eachindependently selected from the group consisting of H, F and ringsystems having a solitary ring or from 2 to 3 fused or linked rings,said ring system being substituted or unsubstituted, said ring systemhaving from 3 to 34 carbons, including carbons of substituents; with theprovisos that if L¹ is a direct link, R^(a) is a ring system and if L²is a direct link, R^(b) is a ring system.
 35. A toner according to claim34 wherein said sulfonamide has the general structure ##STR73## whereinR¹ is O or S;L¹ and L² are each independently a direct link or divalentalkyl or fluoroalkyl having from 1 to 20 carbons; R^(a) and R^(b) areeach a ring system having a single ring or from 2 to 3 fused or linkedrings, said ring system having from 6 to 34 carbons.
 36. A toneraccording to claim 35 wherein R¹ is O.
 37. A toner according to claim 36wherein at least one of R^(a) and R^(b) is substituted by tertiary alkylhaving from 4 to 20 carbons.
 38. A toner according to claim 36 whereinone of R^(a) and R^(b) is substituted by at least one electronwithdrawing group and the other one of R^(a) and R^(b) is substituted byat least one tertiary alkyl having from 4 to 20 carbons, with theproviso that the number of electron withdrawing groups is equal to orless than the number of t-alkyls.
 39. A toner according to claim 36wherein at least one of R^(a) and R^(b) is phenyl having two t-butylsubstituents and a third substituent selected from the group consistingof NO₂, OH, NH₂, N(CH₃)₂, alkyl having from 1 to 8 carbons, and alkoxyhaving from 1 to 8 carbons.